Doped polar layers and semiconductor device incorporating same

ABSTRACT

The disclosed technology generally relates to ferroelectric materials and semiconductor devices, and more particularly to semiconductor memory devices incorporating doped polar materials. In one aspect, a semiconductor device comprises a capacitor which in turn comprises a polar layer comprising a base polar material doped with a dopant. The base polar material includes one or more metal elements and one or both of oxygen or nitrogen. The dopant comprises a metal element that is different from the one or more metal elements and is present at a concentration such that a ferroelectric switching voltage of the capacitor is different from that of the capacitor having the base polar material without being doped with the dopant by more than about 100 mV. The capacitor stack additionally comprises first and second crystalline conductive oxide electrodes on opposing sides of the polar layer. The capacitor stack further comprises first and second barrier metal layers on respective ones of the first and second crystalline conductive oxide electrodes on opposing sides of the polar layer

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/842,593, filed Apr. 7, 2020, which claims the benefit of priority toU.S. Provisional Patent Application No. 62/831,044, filed Apr. 8, 2019.The content of each of these applications is hereby incorporated byreference herein in its entirety.

BACKGROUND Field

The disclosed technology generally relates to ferroelectric materialsand semiconductor devices incorporating the same, and more particularlyto semiconductor memory devices incorporating ferroelectric capacitors.

Description of the Related Art

Memory devices can be volatile or nonvolatile. Generally, volatilememory devices may have certain advantages, while nonvolatile memorydevice may have certain other advantages. For example, while somenonvolatile memory devices such as floating gate-based memory devices(e.g., flash memory device) may advantageously retain data withoutpower, such devices may have relatively slow access times and limitedcycling endurance. Conversely, while some volatile memory device such asdynamic random access memory (DRAM) may advantageously have relativelyaccess times and higher cycling endurance, such devices lose data whenpowered off.

In some DRAM technologies, memory cells are arranged in a devicearchitecture that includes a cell capacitor connected to the drain of anaccess transistor. In these technologies, memory states are stored inthe cell capacitor. For example, stored charge in the cell capacitor mayrepresent a logical state “1”, while a lack of stored charge in thecapacitor may represent a logical state “0”. Writing may be accomplishedby activating the access transistor, and draining the cell capacitor ofits charge to write a “0”, or charging the cell capacitor to write a“1”. Reading may be accomplished in a similar manner by sensing thecharge state of the cell capacitor using a sense amplifier to determinethe memory state. If a pulse of charge is detected by the amplifier, thecell held a charge and thus reads “1”, while a lack of such a pulseindicates a “0”. In DRAM, the read process is destructive because if thecapacitor was charge in the “1” state, it must be re-charged to restorethe state. In addition, as the device footprint scales with advancingtechnology nodes, there is an increasing need to increase the dielectricconstant while reducing the leakage current of the dielectric of thecapacitor. Furthermore, even when powered, because the capacitor losesits charge after some time due to leakage, a DRAM cell is activelyrefreshed at intervals to restore the memory state. There is need for amemory device that provides an advantage over conventional volatile andnonvolatile memory technologies.

SUMMARY

In a first aspect, a semiconductor device comprises a capacitorcomprising a polar layer comprising a base polar material doped with adopant, wherein the base polar material includes one or more metalelements and one or both of oxygen or nitrogen, and wherein the dopantcomprises a metal element that is different from the one or more metalelements and is present at a concentration such that a ferroelectricswitching voltage of the capacitor is different from that of thecapacitor having the base polar material without being doped with thedopant by more than about 100 mV. The capacitor stack additionallycomprises first and second crystalline conductive oxide electrodes onopposing sides of the polar layer. The capacitor stack further comprisesfirst and second barrier metal layers on respective ones of the firstand second crystalline conductive oxide electrodes on opposing sides ofthe polar layer.

In a second aspect, a semiconductor device comprises a capacitor stackcomprising a polar layer comprising a base polar material doped with adopant, wherein the base polar material includes one or more metalelements and one or both of oxygen or nitrogen, and wherein the dopantcomprises a metal element of one of 4d series, 5d series, 4f series or5f series that is different from the one or more metal elements, whereinthe dopant is present at a concentration such that a remnantpolarization of the polar layer is different than that of the base polarmaterial without the dopant. The capacitor stack further comprises firstand second crystalline conductive oxide electrodes on opposing sides ofthe polar layer. The semiconductor device further comprises first andsecond barrier metal layers on respective ones of the first and secondcrystalline conductive oxide electrodes on opposing sides of the polarlayer.

In a third aspect, a semiconductor device comprises a capacitorcomprising a polar layer comprising a base polar material doped with adopant, wherein the base polar material includes one or more metalelements and one or both of oxygen or nitrogen, wherein the dopantcomprises a metal element that is different from the one or more metalelements and is present at a concentration such that a remnantpolarization of the polar layer is different from that of the base polarmaterial without the dopant by more than about 5 μC/cm². The capacitorstack additionally comprises first and second crystalline conductiveoxide electrodes on opposing sides of the polar layer. The capacitorstack further comprises first and second barrier metal layers onrespective ones of the first and second crystalline conductive oxideelectrodes on opposing sides of the polar layer.

In a fourth aspect, a capacitor comprises a crystalline polar layercomprising a base polar material substitutionally doped with a dopant.The base polar material comprises one or more metal elements and one orboth of oxygen or nitrogen. The dopant comprises a metal element of oneof 4d series, 5d series, 4f series or 5f series that is different fromthe one or more metal elements, such that a ferroelectric switchingvoltage of the capacitor is different from that of the capacitor havingthe base polar material without being doped with the dopant by more thanabout 100 mV.

In a fifth aspect, a capacitor comprises a crystalline polar layercomprising a base polar material substitutionally doped with a dopant.The base polar material comprises a base metal oxide having a chemicalformula ABO₃, wherein each of A and B represents on or more metalelements occupying interchangeable atomic positions of a crystalstructure of the base polar material. The dopant comprising a metalelement of one of 4d series, 5d series, 4f series or 5f series that isdifferent from the one or more metal elements of the base polarmaterial. The capacitor additionally comprises first and secondcrystalline conductive oxide electrodes on opposing sides of the polarlayer. The crystalline polar layer has one of a perovskite structure, ahexagonal crystal structure or a superlattice structure.

In a sixth aspect, a capacitor comprises a crystalline polar layercomprising a base polar material substitutionally doped with a dopant.The base polar material comprises one or more metal elements and one orboth of oxygen or nitrogen. The dopant comprises a metal element of oneof 4d series, 5d series, 4f series or 5f series that is different fromthe one or more metal elements, wherein the dopant is present at aconcentration such that a remnant polarization of the polar layer isdifferent than that of the base polar material without the dopant bymore than about 5 μC/cm².

In a seventh aspect, a semiconductor device comprises a capacitor, whichin turn comprises a polar layer comprising a crystalline base polarmaterial doped with a dopant. The base polar material includes one ormore metal elements and one or both of oxygen or nitrogen, wherein thedopant comprises a metal element that is different from the one or moremetal elements and is present at a concentration such that aferroelectric switching voltage of the capacitor is different from thatof the capacitor having the base polar material without being doped withthe dopant by more than about 100 mV. The capacitor stack additionallycomprises first and second crystalline conductive or semiconductiveoxide electrodes on opposing sides of the polar layer, wherein the polarlayer has a lattice constant that is matched within about 20% of alattice constant of one or both of the first and second crystallineconductive or semiconductive oxide electrodes. The first crystallineconductive or semiconductive oxide electrode serves as a template forgrowing the polar layer thereon, such that at least a portion of thepolar layer is pseudomorphically formed on the first crystallineconductive or semiconductive oxide electrode.

In an eighth aspect, a semiconductor device comprises a capacitor, whichin turn comprises a crystalline polar layer comprising a base polarmaterial substitutionally doped with a dopant. The base polar materialcomprises a metal oxide having one of a perovskite structure or ahexagonal crystal structure. The dopant comprises a metal of one of 4dseries, 5d series, 4f series or 5f series that is different frommetal(s). The capacitor stack further comprises first and secondcrystalline conductive or semiconductive oxide electrodes on opposingsides of the crystalline polar layer, wherein the crystalline polarlayer has the same crystal structure as one or both of the first andsecond crystalline conductive or semiconductive oxide electrodes.

In a ninth aspect, a semiconductor device comprises a capacitor, whichin turn comprises a polar layer comprising a crystalline base polarmaterial doped with a dopant, wherein the base polar material includesone or more metal elements and one or both of oxygen or nitrogen,wherein the dopant comprises a metal element that is different from theone or more metal elements and is present at a concentration such that aremnant polarization of the polar layer is different from that of thebase polar material without the dopant by more than about 5 μC/cm², Thecapacitor stack additionally comprises first and second crystallineconductive or semiconductive oxide electrodes on opposing sides of thepolar layer, wherein the polar layer has a lattice constant that ismatched within about 20% of a lattice constant of one or both of thefirst and second crystalline conductive or semiconductive oxideelectrodes. The first crystalline conductive or semiconductive oxideelectrode serves as a template for growing the polar layer thereon, suchthat at least a portion of the polar layer is pseudomorphically formedon the first crystalline conductive or semiconductive oxide electrode.

In a tenth aspect, a semiconductor device comprises a transistor formedon a silicon substrate and a capacitor electrically connected to thetransistor by a conductive via. The capacitor comprises upper and lowerconductive oxide electrodes on opposing sides of a polar layer, whereinthe lower conductive oxide electrode is electrically connected to adrain of the transistor. The capacitor additionally comprises a polarlayer comprising a base polar material doped with a dopant, wherein thebase polar material includes one or more metal elements and one or bothof oxygen or nitrogen, wherein the dopant comprises a metal element thatis different from the one or more metal elements and is present at aconcentration such that a ferroelectric switching voltage of thecapacitor is different from that of the capacitor having the base polarmaterial without being doped with the dopant by more than about 100 mV.The semiconductor device additionally comprises a lower barrier layercomprising a refractory metal or an intermetallic compound between thelower conductive oxide electrode and the conductive via.

In an eleventh aspect, a semiconductor device comprises a transistorformed on a silicon substrate and a capacitor electrically connected tothe transistor by a conductive via. The capacitor comprises upper andlower conductive oxide electrodes on opposing sides of a polar layer,wherein the lower conductive oxide electrode is electrically connectedto a drain of the transistor. The capacitor additionally comprises thepolar layer comprising a base polar material doped with a dopant,wherein the base polar material includes one or more metal elements andone or both of oxygen or nitrogen, and wherein the dopant comprises ametal element of one of 4d series, 5d series, 4f series or 5f seriesthat is different from metal(s) of the metal oxide that is present at aconcentration such that a remnant polarization of the polar layer isdifferent than that of the base polar material without the dopant. Thesemiconductor device additionally comprises a barrier sealant layerformed on one or both side surfaces of one or more of the polar layer,the upper conductive oxide electrode layer and the lower conductiveoxide electrode layer.

In a twelfth aspect, a semiconductor device comprises a capacitorcomprising a ferroelectric oxide layer interposed between first andsecond conductive oxide electrode layers, wherein the ferroelectricoxide layer comprises a base ferroelectric oxide that is doped with adopant, wherein the dopant lowers a remnant polarization of the baseferroelectric oxide relative to an undoped base ferroelectric oxide byat least 5%.

In a thirteenth aspect, a semiconductor device comprises a ferroelectricoxide layer interposed between first and second conductive oxideelectrode layers, wherein the ferroelectric oxide layer has a latticeconstant that is matched within about 20% of a lattice constant of oneor both of the first and second conductive oxide electrode layers.

In a fourteenth aspect, a semiconductor device comprises a capacitorcomprising a ferroelectric oxide layer interposed between first andsecond conductive oxide electrode layers, wherein the ferroelectricoxide layer undergoes a ferroelectric transition at a voltage lower thanabout 600 mV across the capacitor.

In a fifteenth aspect, a semiconductor device comprises a capacitorcomprising a ferroelectric oxide layer interposed between first andsecond conductive oxide electrode layers, wherein the ferroelectricoxide layer has a thickness less than about 50 nm.

In a sixteenth aspect, a semiconductor device comprises a ferroelectricoxide layer having a remnant polarization greater than about 10 μC/cm²,wherein the ferroelectric oxide layer is doped with a lanthanide elementat a concentration greater than about 5.0% on the basis of a totalnumber of atomic sites of a metal of the ferroelectric oxide layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A schematically illustrates a side view of a capacitor comprisinga polar layer interposed between first and second conductive oxideelectrode layers, according to various embodiments.

FIG. 1B schematically illustrates a polarization-field (P-E) loop of aferroelectric capacitor comprising a ferroelectric layer, indicatingpolarization changes associated with non-switching and switching.

FIG. 1C schematically illustrates a temporal current response of aferroelectric capacitor associated with non-switching and switching.

FIG. 2A schematically illustrates a perovskite crystal structure of apolar layer of a capacitor, according to some embodiments.

FIG. 2B schematically illustrates a hexagonal crystal structure andatomic displacements associated with switching of a polar layer,according to some embodiments.

FIG. 2C schematically illustrates a superlattice crystal structure andatomic displacements associated with switching of a polar layer,according to some embodiments.

FIG. 3 schematically illustrates crystal structures of layers of acapacitor comprising first and second conductive oxide electrode layersand a polar layer interposed therebetween having matching crystalstructures, according to various embodiments.

FIG. 4A schematically illustrates a polarization-field (P-E) loop with ahysteresis, an associated double well of a free energy curve andassociated atomic displacements corresponding to ferroelectrictransitions between polarization states of a ferroelectric material.

FIG. 4B schematically illustrates a free energy curve exhibiting adouble well of a free energy curve and associated atomic displacementscorresponding to ferroelectric transitions in a ferroelectric materialhaving a perovskite crystal structure.

FIG. 4C is a graph showing calculations of a free energy curve of aferroelectric layer formed by doping a base ferroelectric material withvarying amounts of a dopant, thereby tuning the double well of the freeenergy curve, according to embodiments.

FIG. 5 schematically illustrates energy considerations of switching andnonvolatile storage in a ferroelectric memory device, according toembodiments.

FIG. 6 illustrates a schematic perovskite crystal structure of a polarlayer doped with a dopant A′ that can replace atoms of the metal Aoccupying corner positions in a base polar material having a chemicalformula ABO₃, according to embodiments.

FIG. 7 illustrates a schematic perovskite crystal structure of polarlayer doped with a dopant B′ that can replace atoms of the metal Boccupying the center position in a base polar material having a chemicalformula ABO₃, according to embodiments.

FIG. 8A illustrates a side view of a capacitor comprising a polar layerinterposed between first and second conductive oxide electrode layers,according to embodiments.

FIG. 8B illustrates a side view of a capacitor comprising a polar layerinterposed between first and second conductive oxide electrode layers,and first and second barrier layers, according to embodiments.

FIG. 8C illustrates a side view of a capacitor comprising a polar layerinterposed between first and second conductive oxide electrode layers,first and second barrier layers, and sealant barrier layers formed onvertical sidewalls of the capacitor, according to embodiments.

FIG. 9 illustrates a cross-sectional view of a memory device comprisinga transistor coupled to a capacitor comprising a polar layer interposedbetween first and second conductive oxide electrodes, according toembodiments.

FIG. 10 illustrates an perspective view of a memory device comprising afinFET transistor coupled to a capacitor comprising a polar layerinterposed between first and second conductive oxide electrodes,according to embodiments.

DETAILED DESCRIPTION

The demand for higher performance and lower price for semiconductormemories continue to grow for various applications, including highperformance, high reliability and/or portable computing devices. Forstorage applications, due considerations including power-consumption,size and shock/vibration tolerance capability, solid state memorydevices have been replacing hard disk drives for various applications.

The demand for memories with lower power, faster access speed andincreasing memory capacity is reflected by the increasing demand forembedded memories. An embedded memory is integrated on-chip with otherunits such as microprocessors. Some embedded memories have a potentialas a low power and high performance device because the memory isdirectly integrated to the logic circuits and analog components viaon-chip bus, which can enable enhanced parallel processing. A furtherbenefit of some embedded memories is the reduction of the number ofchips enabled by higher level of integration, resulting in lower packagecost and smaller number of pins per chip.

For nonvolatile memories including embedded nonvolatile memories, thedesirable characteristics include low power operation, fast write/readtimes, a near infinite number of write/read cycles, compatibility withSi fabrication processes, non-volatility and lower added process costfor adding memory cells to logic circuitry.

The non-volatility is particularly helpful in reducing standby memorypower. For some applications, e.g., high density standalone memoryapplications, smaller cell size is desirable to reduce cost. For someother applications, e.g., embedded memories, it may be more important toachieve desirable electrical properties than to realize a high densityof the memory cells.

Conventional non-volatile memories such as flash memory or electricallyerasable programmable read-only memory (EEPROM) only partially fulfilthese demands. While they are nonvolatile, write/erase cycles aretypically limited by about million cycles. In addition, write/erasetimes, voltage, energy and power consumption substantially exceed thoseof random access memories such as static random access memory (SRAM) anddynamic random access memory (DRAM).

Some embedded memories are based on SRAM. While added process cost isrelatively small, SRAM is a volatile memory having a relatively largecell size and consumes relatively high standby power. Some otherembedded memories are based on DRAM. While DRAM offers smaller cell sizethan SRAM, the added process cost is higher and it also consumesrelatively high standby power.

Advantageous features of both volatile and nonvolatile memorytechnologies may be realized by employing a capacitor comprising aferroelectric layer in a semiconductor memory device, e.g., aferroelectric random access memory (FeRAM). FIG. 1A schematicallyillustrates a side view of a capacitor 100 comprising a storage layer104, e.g., a ferroelectric layer, interposed between first and secondconductive oxide electrode layers 108, 112, according to variousembodiments. Unlike a DRAM cell capacitor in which a dielectric having alinear polarization-field (P-E) response may be used, the capacitor 100includes a ferroelectric layer, which has a nonlinear P-E response. Asdescribed herein, a ferroelectric phenomenon refers to a phenomenon inwhich a crystal exhibits a spontaneous electric polarization in whichthe direction of the polarization can be reoriented betweencrystallographically defined states under an external electric field.When an external electric field is applied across the ferroelectricmaterial, dipoles produced by small shifts in the positions of atoms ormolecules shifts in the distributions of electronic charge in thecrystal structure tend to align themselves with the field direction.After the charge is removed, the dipoles retain their polarizationstate, thereby exhibiting a remnant (sometimes referred to as remnant)polarization.

FIG. 1B schematically illustrates a polarization-field (P-E) loop 120 ofa capacitor such as the capacitor 100 illustrated with respect to FIG.1A comprising a storage layer 104, e.g., a ferroelectric layer. The P-Eloop 120 may represent that of the ferroelectric layer comprising apolydomain ferroelectric material. In the illustrated P-E loop 120,prior to polarization for the first time, there may initially be astatistical distribution of ferroelectric domains such that the netpolarization at zero field is about zero. The initial polarization (P)may be represented by a P-E curve portion 122. When the ferroelectriclayer is polarized for the first time by applying a positive electricfield, starting with a polarization P=0, the polarization increases withincreasing field until it reaches saturation at +Pmax. After thesaturation is reached at +Pmax, when the electric field is subsequentlyreduced according to a P-E curve portion 124, at E=0, a polarization mayremain. The remaining polarization is referred to herein as a remnantpolarization (+Pr). In order to bring the polarization back to zero, anegative electric field may be applied. A sufficient electric field forreducing the polarization back to zero is referred to herein as acoercive field (Ec). According to the P-E curve portion 124, a negativecoercive field (−Ec) may be applied to reduce the polarization to zerofrom the +Pr. If the negative voltage or field is further increased inmagnitude, then the hysteresis loop behaves similarly to that under apositive but in a reverse sense. That is, the negative P increases inmagnitude with increasing negative electric field until it reachessaturation at −Pmax. Subsequently, when the electric field issubsequently reduced in magnitude along a P-E curve portion 126, at E=0,a remnant polarization −Pr may remain. Thus, the ferroelectric layerexhibits a characteristic of a remnant polarization +/−Pr, which can bereversed by an applied electric field in the reverse direction, whichgives rise to a hysteretic P-E loop in ferroelectric capacitors.

By using thin film technologies, operation fields or voltages may bereduced to a level below standard chip supply voltages. FeRAM uses theP-E characteristic to hold data in a non-volatile state and allows datato be rewritten fast and frequently. Thus, a FeRAM has the advantageousfeatures of both volatile and nonvolatile memory technologies.

Still referring to FIG. 1B, in various FeRAM devices, voltage pulses areused to write and read the digital information. If an electric fieldpulse is applied in the same direction as the remnant polarization, noswitching may occur. A change in polarization ΔP_(NS) between Pmax andPr may be present due to the dielectric response of the ferroelectricmaterial. On the other hand, if an electric field pulse is applied inthe opposite direction as the remnant polarization, switching may occur.For example, if the initial polarization is in the opposite direction asthe applied electric field, the polarization of the ferroelectric layerreverses, giving rise to an increased switching polarization change ΔPs.

FIG. 1C schematically illustrates temporal current response curves 144and 140 associated with non-switching and switching, respectively, of aferroelectric capacitor such as the capacitor 100 including aferroelectric layer as the storage layer 104 in FIG. 1A. The differentstates of the remnant polarization (+Pr and −Pr) illustrated above withrespect to FIG. 1B can cause different transient current behavior of theferroelectric capacitor to an applied voltage pulse. Based on adifference in current-time responses, e.g., instantaneous current,integrated current, rate of change in current, etc., the variousparameters associated with switching between states corresponding toremnant polarizations +P and −P can be determined. For example, theswitched charge ΔQs and the non-switch charge ΔQ_(NS) can be determinedby integrating the current response curves 140 and 144, respectively. Adifference in charge ΔQ=AΔP (where A is the area of capacitor) enablesdistinguishing of the two logic states.

Using the states having the remnant polarization (Pr and −Pr), FeRAM canbe implemented as a nonvolatile memory, which is an advantage over aDRAM. The nonvolatility of the stored information can in turn reduce theenergy consumption, e.g., by reducing or eliminating refresh. FeRAM alsooffers advantages over some nonvolatile memory technologies such asflash memory. For example, FeRAM can offer much higher cycling endurancecompared to flash memory, by several orders of magnitude. FeRAM can alsooffer faster write times (few to tens of nanoseconds) compared to flashmemory by several orders of magnitude. FeRAM can also offer write andread voltages that are fractions of those of flash memory.

For enhanced reliability as a nonvolatile memory, the remnantpolarization of the ferroelectric layer should be suitably high becauseit is proportional to the switching charge. For example, for sub 100 nmnodes, when the switching charge of a ferroelectric capacitor, which maybe expressed as ΔQ=AΔP, where A is the area of the capacitor and ΔP isthe switching polarization, falls below a threshold value of about 30fC, 25 fC, 20 fC, 15 fC, 10 fC, 5 fC, or a value in a range between anyof these values, a read failure may result. For nonvolatile memorydevices in sub 100 nm nodes according to various embodiments, aswitching polarization ΔP corresponding to a switching charge may beabout 20-60 μC/cm², 60-100 μC/cm², 50-140 μC/cm², 140-180 μC/cm²,180-220 μC/cm², 220-260 μC/cm², or a value in a range between any ofthese values, corresponding to remnant polarization Pr>10 μC/cm², e.g.,10-30 μC/cm², 30-50 μC/cm², 50-70 μC/cm², 70-90 μC/cm², 90-110 μC/cm²,110-130 μC/cm², or a value in a range between any of these values.

For low power nonvolatile memory devices according to embodiments, a lowcoercive voltage is advantageous for low power and/or energy switchingof the ferroelectric capacitor. For example, for various low powersystems, e.g., systems having integrated therein FeRAM as an embeddedmemory, the coercive voltage (Ec) may be about 1200 mV, 1100 mV, 1000mV, 900 mV, 800 mV, 700 mV, 600 mV, 500 mV, 400 mV, 300 mV, 200 mV, or avalue in a range between any of these values.

Despite these advantages, for the small cell sizes in advancedtechnology nodes (e.g., sub 100 nm nodes), achieving relatively highremnant polarization (e.g., 10 μC/cm² for sufficient ON/OFF ratio, readwindow and nonvolatility) and relatively low coercive voltage (e.g.,lower than about 1200 mV) for ultra-low voltage operation (e.g., lowerthan about 1200 mV) and nonvolatility (e.g., sufficient read windowafter 10 years at room temperature) for some applications have beendifficult. For example, while a lower coercive voltage may be achievedby reducing the film thickness for some materials to an extent,decreasing the film thickness below a certain thickness may increase thecoercive field in many ferroelectric materials, thereby failing to lowerthe coercive voltage. Thus, for each individual case, the thicknessscaling may not be sufficient. To address these and other needs, in thedisclosed technology, a ferroelectric capacitor for memory applicationsis disclosed, which can switch at ultra-low voltages (e.g., <1200 mV)while simultaneously displaying relatively high remnant polarization(e.g., >10 μC/cm²).

The inventors have discovered that, to achieve these and other desirableperformance parameter for nonvolatile memory applications, e.g., anFeRAM, a combination of various capacitor elements has to be engineeredin conjunction. In particular, referring to FIG. 1A, the capacitor 100comprises a storage layer 104 interposed between an upper or firstconductive oxide electrode layer 108 and a lower or second conductiveoxide electrode layer 112. According to various embodiments, the storagelayer 104 comprises an engineered polar layer. The polar layer isengineered by providing a base polar material and doping the base polarmaterial with a dopant. The base polar material includes one or moremetal elements and one or both of oxygen or nitrogen. In someembodiments, the dopant comprises a metal element that different fromthe one or more metal elements and is present at a concentration suchthat a ferroelectric switching voltage of the capacitor is differentfrom that of the capacitor having the base polar material without beingdoped with the dopant by more than about 100 mV. In some otherembodiments, the dopant comprises a metal element of one of 4d series,5d series, 4f series or 5f series that is different from the one or moremetal elements and is present at a concentration such that a remnantpolarization of the polar layer is different than that of the base polarmaterial without the dopant. In some embodiments, the dopant comprises ametal element that different from the one or more metal elements and ispresent at a concentration such that a remnant polarization of the polarlayer is different than that of the base polar material without thedopant by more than about 5 μC/cm². The capacitor 100 stack additionallycomprises first and second conductive oxide electrode layers 108, 112that are engineered in conjunction with the storage layer 104, e.g.,with respect to the crystal structure, composition, thickness andstacking with further electrodes thickness. In some embodiments, thecapacitor 100 further comprises first and second barrier metal layers onrespective ones of the first and second crystalline conductive oxideelectrodes on opposing sides of the polar layer.

The base polar material may be a dielectric material, a paraelectricmaterial or a ferroelectric material, as described herein.

As described herein, dielectrics refer to electrical insulators thatsubstantially do not conduct electricity because they have no or verylittle free electrons to conduct electricity. A dielectric can bepolarized by applying an electric field. Dielectrics can be classifiedinto polar dielectrics and nonpolar dielectrics.

As described herein, a polar insulator or a polar material refers to anelectrically insulating material having unit cells or molecular unitsthat have a permanent electric dipoles moment. In these materials, inthe absence of an external electric field, the polar molecular units arerandomly oriented. As the result, in the absence of an external fielddisplay substantially no net dipole moment. When an external electricfield is applied, the dipoles can align themselves with the externalelectric field such that a net dipole moment is produced.

As described herein, a non-polar insulator or a non-polar materialrefers to an electrically insulating material having unit cells ormolecular units that do not have a permanent electric dipole moment. Inthese materials, in the absence of an external electric field, thecenter of positive charge coincides with the center of negative chargein the unit cells such that the molecules have substantially no netdipole moment. When an electric field is applied, positive chargeexperiences a force in the direction of electric field and negativecharge experiences a force in the direction opposite to the field, suchthat the unit cells include dipoles therein, referred to as induceddipoles.

As described herein, a material that undergoes a dielectricpolarization, or a dielectric material, refers to an insulating materialwhich, when polarized, the induced polarization varies substantiallylinearly proportional to the applied external electric field. That is,unlike the P-E curve described above with respect to FIG. 1B, adielectric material exhibits a substantially linear P-E response. Thus,the electric permittivity, corresponding to the slope of thepolarization curve, can be a constant as a function of the externalelectric field.

As described herein, a material that undergoes a paraelectricpolarization, or a paraelectric material, refers to an insulatingmaterial which, when polarized, the induced polarization variessubstantially nonlinearly with E. That is, the material exhibits asubstantially nonlinear P-E curve. Thus, the electric permittivity,corresponding to the slope of the polarization curve, is not a constantas in a paraelectric material but varies as a function of the externalelectric field. However, unlike the P-E curve described above withrespect to FIG. 1B, a paraelectric material does not exhibit ahysteresis.

As described herein, a material that undergoes a ferroelectricpolarization, or a ferroelectric, refers to an insulating materialwhich, when polarized, the induced polarization varies substantiallynonlinearly with E. In addition to displaying a nonlinear P-E curve asin a paraelectric material, as described above with respect to FIG. 1B,a material that undergoes a ferroelectric polarization, or aferroelectric material, refers to an insulating material whichdemonstrates a remnant nonzero polarization even when the E is zero.Thus, the material exhibits a substantially nonlinear P-E curve having ahysteresis, as described above with respect to FIG. 1G. A distinguishingfeature of a ferroelectric material includes reversal in polarity of theremnant polarization by a suitably strong applied E in the oppositedirection. Thus, the polarization is therefore dependent not only on thecurrent electric field but also on its history, thereby displaying ahysteresis loop, as discussed above with respect to FIG. 1B.

Some ferroelectric materials demonstrate substantial ferroelectricitybelow a certain phase transition temperature, referred to as the Curietemperature (T_(C)), while demonstrating paraelectricity above thistemperature. Above the T_(C), the remnant polarization vanishes, and theferroelectric material transforms into a paraelectric material. Manyferroelectrics lose their piezoelectric properties above T_(C)completely, because their paraelectric phase has a centrosymmetriccrystal structure. Accordingly, as described herein, unless describedotherwise, a material described as having a remnant polarization, e.g.,a ferroelectric material, refers to the material below the T_(C).

Doped Polar Layers for Semiconductor Devices

To achieve the above performance parameters of a capacitor, according tovarious embodiments, a semiconductor device, e.g., a memory device,includes a capacitor, e.g., a capacitor 100 arranged as illustrated inFIG. 1A. The capacitor comprises a storage layer 104, which in turncomprises a crystalline polar layer comprising a base polar materialthat is doped, e.g., substitutionally doped, with a dopant. In someembodiments, the base polar material includes one or more metal elementsand one or both of oxygen or nitrogen. The dopant comprises a metalelement of one of 4d series, 5d series, 4f series or 5f series that isdifferent from the one or more metal elements. The dopant is present ata concentration such that a remnant polarization of the polar layer isdifferent than that of the base polar material without the dopant bymore than about 5 μC/cm². In some other embodiments, the base polarmaterial comprises a base metal oxide having a chemical formula ABO₃,wherein each of A and B represents on or more metal elements occupyinginterchangeable atomic positions of a crystal structure of the basepolar material. The dopant comprising a metal element of one of 4dseries, 5d series, 4f series or 5f series that is different from the oneor more metal elements. The capacitor additionally comprises first andsecond crystalline conductive oxide electrodes on opposing sides of thepolar layer. The crystalline polar layer has one of a perovskitestructure, a hexagonal crystal structure or a superlattice structure.The capacitor stack additionally comprises first and second crystallineconductive oxide electrodes 108, 112, that is engineered in conjunctionwith the storage layer 104, e.g., with respect to the crystal structureand/or composition.

According to various embodiments, the base polar material comprises abase ferroelectric material, a base paraelectric material, a dielectricmaterial, or a combination thereof. Doping the base polar materialaccording to embodiments disclosed herein changes the ferroelectriccharacteristics of the base polar material.

In some embodiments, when the base polar material comprises a baseferroelectric material, increasing the concentration of the dopantdecreases the remnant polarization of the base ferroelectric material.In these embodiments, the polar layer is a ferroelectric layer but has aremnant polarization that is lower than it would be without the presenceof the dopant. For example, the concentration of the dopant the may bepresent at a concentration such that the polar layer is a paraelectriclayer having substantially zero remnant polarization. However,embodiments are not so limited and in other embodiments, when the basepolar material comprises a base ferroelectric material, increasing theconcentration of the dopant increases the remnant polarization of thebase ferroelectric material. In these embodiments, the polar layer is aferroelectric layer but has a remnant polarization that is higher thanit would be without the presence of the dopant.

In some embodiments, when the base polar material comprises a baseparaelectric material or a base dielectric material, increasing theconcentration of the dopant increases the remnant polarization of thebase paraelectric material or the base dielectric material. In theseembodiments, the dopant comprises an element and is present at aconcentration such that the base paraelectric material or the basedielectric material is converted to a ferroelectric material, and theresulting polar layer is a ferroelectric layer. However, embodiments arenot so limited and in other embodiments, when the base polar materialcomprises a base ferroelectric material, increasing the concentration ofthe dopant may not result in an increases the remnant polarization ofthe base ferroelectric material. In these embodiments, the dopantcomprises an element and is present at a concentration such that thebase paraelectric material or the base dielectric material is notconverted to a ferroelectric material, such that the resulting polarlayer is a paraelectric or dielectric layer.

From a device point of view, it can be important for the storage layer104 to undergo substantially complete switching between stable states,e.g., between +Pr and −Pr states to obtain unambiguous digitalinformation. The substantial complete switching may be achieved bysufficiently high field and sufficiently long pulse width. Switchingtime depends on many factors, e.g., domain structure, nucleation rate ofenergetically favorable ferroelectric domains, the mobility of theferroelectric domain walls, to name a few. Without being bound to anytheory, a lower limit for the switching time (to), assuming sufficientfield greater than the coercive field is applied, can be related to thetime for a ferroelectric domain wall to propagate from one electrode toanother in a capacitor film with a thickness (d) by:

t ₀ =d/c,

where c is the velocity of the domain wall. The velocity of the domainwall can correspond to the speed of sound (˜4000 m/s). For example, fora 200 nm thick polar layer, to can be about 50 ps. However, conventionalferroelectric stacks, e.g., using Pt electrodes, can display a thicknesseffect, where a reduction in the thickness d can reduce the switchingtime only to an extent, while a further reduction may not result in areduction in the switching speed. Without being bound to any theory,such effect can be attributed to a variety of factors, includingincreasing effective coercive field with decreasing d, which can in turnbe caused by an interfacial dielectric layer that forms between thepolar layer and the electrode(s). Such interfacial layer can give riseto charge injection effects into the interfacial layers, leading toscreening effects, which increases the effective coercive field. Thus,to enable fast (e.g., <20 ns) and low voltage (e.g., <1200 mV) switchingof a ferroelectric capacitor according to various embodiments describedherein, the inventors have optimized the thickness, the composition ofthe doped polar layer and the oxide electrodes (e.g., having a crystalstructure matching the doped polar layer), as described herein.

To enable these and other advantages, in various embodiments disclosed,herein, the storage layer 104 (FIG. 1A) is a ferroelectric layer asdoped and advantageously undergoes a ferroelectric transition at avoltage across the storage layer 104, which may correspond to thecoercive voltage, that is lower than about 1200 mV, 1100 mV, 1000 mV,900 mV, 800 mV, 700 mV, 600 mV, 500 mV, 400 mV, 300 mV, 200 mV, 100 mV,or a voltage in a range defined by any of these voltages. In someembodiments, these low voltages may be achieved while simultaneouslydisplaying relatively high remnant polarization (e.g., >10 μC/cm²). Thecombination of relatively low voltage ferroelectric transition and therelatively high remnant polarization is achieved through variouscombinations of features describe herein.

In various embodiments disclosed herein, the storage layer 104 (FIG. 1A)is a ferroelectric layer and is formed from a base ferroelectricmaterial having a relatively high starting remnant polarization,e.g., >10 μC/cm², that is doped with a dopant, wherein the dopant lowersa remnant polarization of the base ferroelectric material relative to anundoped base ferroelectric material by at least 5%.

In various embodiments disclosed herein, the storage layer 104 (FIG.1A), which may have a matched crystal structure to the polar layer, hasa lattice constant that is matched within about 25%, 20%, 15%, 10%, 5%,2%, 1%, or a percentage in a range defined by any of these values, of alattice constant of one or both of the first and second conductive oxideelectrode layers 108, 112. At least portions of the storage layer 104and one or both of the first and second conductive oxide electrodelayers 108, 112 may be pseudomorphic.

Accordingly, according to various embodiments disclosed herein, toenable fast and low voltage switching, the storage layer 104 has athickness less than about 200 nm, 150 nm, 100 nm, 50 nm, 20 nm, 10 nm, 5nm, 2 nm, or a thickness in a range defined by any of these values. Insome implementations, these the thickness may be a critical parametersuch that when the thickness is outside these values, the desiredswitching voltage and/or switching time may not be achieved.

In addition, in various embodiments disclosed herein, the storage layer104 is doped with a dopant at a concentration greater than about 5.0% onthe basis of a total number of metal atoms of the ferroelectric oxidelayer. The doped storage layer 104 has a remnant polarization that isdifferent from an the storage layer 104 having the same compositionwithout the dopant by greater than about 5 μC/cm², and having a finalremnant polarization that is greater than about 10 μC/cm².

As described above, the base polar material may be a dielectricmaterial, a paraelectric material or a ferroelectric material, asdescribed above. As described, in some embodiments, dopants may decreasethe remnant polarization of a base polar material that is aferroelectric material while reducing a double well potential of thefree energy curve. In some other embodiments, dopants may introduce aremnant polarization by doping a base polar material that is aparaelectric material, which may be accompanied by a double wellpotential of the free energy curve. In yet some other embodiments,dopants may introduce a remnant polarization by doping a base polarmaterial that is a dielectric material, which may be accompanied by adouble well potential of the free energy curve. In these embodiments,the base polar material comprises a dielectric material, and the dopantincreases the ferroelectricity of the dielectric material such that thepolar layer has a remnant polarization greater than about 10 μC/cm². Insome embodiments, the dielectric material comprises one or more of anoxide of Hf, Zr, Al, Si or a mixture thereof. In some embodiments, thedielectric material has a chemical formula represented byHf_(1-x)E_(x)O_(y), wherein each of x and y is greater than zero, andwherein E is selected from the group consisting of Al, Ca, Ce, Dy, Er,Gd, Ge, La, Sc, Si, Sr, Sn or Y. In some embodiments, the dielectricmaterial has a chemical formula represented by Al_(1-x)R_(x)N,Ga_(1-x)R_(x)N or Al_(1-x-y)Mg_(x)Nb_(y)N, wherein each of x and y isgreater than zero, and wherein R is selected from the group consistingof Al, Ca, Ce, Dy, Er, Gd, Ge, La, Sc, Si, Sr, Sn or Y.

Crystal Structures and Compositions of Polar Layers for FerroelectricCapacitors

According to various embodiments, the storage layer 104 (FIG. 1A)comprises a crystalline polar layer having a perovskite crystal latticestructure, a hexagonal crystal lattice structure, or a superlatticestructure.

In some embodiments, the polar layer comprises a ferroelectric oxidehaving a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein m, n and z are integers,and wherein one or both of x and y are greater than zero. A and A′ aremetals that occupy interchangeable atomic positions in the crystalstructure and B and B′ are metals that occupy interchangeable atomicpositions in the crystal structure. One or both of the A′ and B′ may bedopants. Thus, in these embodiments, the ferroelectric oxide comprises abase polar material, which may be represented by a base chemical formulaA_(m)B_(n)O_(z), that is doped with one or more dopants A′ and/or B′ tohave the chemical formula A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z).

In the chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z) above, A and B can represent morethan one atom, such that the ferroelectric oxide is a doped solidsolution. That is, in some embodiments, the ferroelectric oxide can berepresented by a generalized formula for a solid solution represented by(A₁, A₂, . . . A_(N))_((m-x))A′_(x)(B₁, B₂, . . .B_(M))_((n-y))B′_(y)O_(z), wherein m, n and z are integers, and whereinone or both of x and y are greater than zero. A₁, A₂, . . . A_(N) aswell as A′ occupy interchangeable atomic positions in the crystalstructure and B₁, B₂, . . . B_(M) as well as B′ occupy interchangeableatomic positions in the crystal structure. One or both of the A′ and B′may be dopants, while A₁, A₂, . . . A_(N) and B₁, B₂, . . . B_(M) arealloying elements. Thus, in these embodiments, the ferroelectric oxidecomprises a base polar material, which may be represented by a basechemical formula (A₁A₂, . . . A_(N))_(m)(B₁, B₂, . . . B_(M))_(n)O_(z),that is doped with one or more dopants A′ and/or B′ to have the chemicalformula (A₁, A₂, . . . A_(N))_((m-x))A′_(x)(B₁, B₂, . . .B_(M))_((n-y))B′_(y)O_(z). In an analogous manner, in the chemicalformula represented by A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), A′ and B′can represent more than one atom, such that the ferroelectric oxide is adoped with multiple dopants, e.g., (A′₁, A′₂, . . . A′_(N))_(x) thatoccupy interchangeable atomic positions, and (B′₁, B′₂, . . .B′_(M))_(y) that occupy interchangeable atomic positions, where each ofA′₁, A′₂, . . . A′_(N) and B′₁, B′₂, . . . B′_(M) can represents adopant. For simplicity of representation as described herein, somechemical compounds may be represented without one or more of thesubscripts x, y, z, m, n, M and N, which compounds will be understood tohave appropriate values of the subscripts to satisfy the chargeneutrality and stoichiometry, among other things. For example, a dopedalloy represented by (A₁, A₂, . . . A_(N))_((m-x))(A′₁, A′₂, . . .A′_(N))_(x)(B₁, B₂, . . . B_(M))_((n-y))(B′₁, B′₂, . . .B′_(M))_(y)O_(z) may represented as (A₁, A₂, . . . A_(N))(A′₁, A′₂, . .. A′_(N))(B₁, B₂, . . . B_(M))(B′₁, B′₂, . . . B′_(M))O, withoutlimitation.

While the dopant(s) A′ and the alloying elements A₁, A₂, . . . A_(N),and the dopant(s) B′ and the alloying elements B₁, B₂, . . . B_(N) mayoccupy respective interchangeable atomic positions in the crystalstructures, the dopant(s) refer to substituted elements havingparticular attributes and technical effects, e.g., ferroelectricproperties, on the resulting polar layer. In particular, as describedherein, a dopant refers to an element that replaces an atom in the basematerial, e.g., substitutionally, where the dopant has an oxidationstate that is different from the atom it replaces. In addition, thedopant is present in a concentration such that a remnant polarization ofthe polar layer is different than that of the base polar materialwithout the dopant by more than about 5 μC/cm², where the effectiveconcentration results in a remnant polarization of the doped polar layerbeing greater than about 5 μC/cm², among other ferroelectric properties.In various embodiments, the dopant may be a metal element of one of 4dseries, 5d series, 4f series or 5f series. In some embodiments, thedopant comprises a lanthanide element or niobium. In addition, thedopants A′ and/or B′ and their concentrations are such that the metalatoms may achieve a spontaneous distortion of atomic position in therange of 0.3-2% on the basis of a lattice constant of a paraelectricphase of the base polar material. In various embodiments, the dopanthaving the above characteristics is present at an effectiveconcentration greater than 0.1 percent and less than 25 percent on thebasis of the total number of metal atoms in the polar layer, and whereinthe polar layer undergoes a ferroelectric transition at a voltage lowerthan about 1200 mV. Additional details of engineering the crystalstructure with dopant(s) to achieve these and other characteristics ofthe polar layer are discussed infra.

Referring to FIG. 2A, according to some embodiments, the crystallinepolar layer has a perovskite structure 204A. The illustrated perovskitestructure 204A represents a crystalline oxide in a paraelectric state,which may have a chemical formula ABO₃, where each of A and B representone or more metal cations and O represents an oxygen anion. Thecrystalline polar layer can have more than one element represented by A(e.g., A₁, A₂, . . . A_(N)) and/or more than one element represented byB (e.g., B₁, B₂, . . . B_(N)), and can be doped with one or more dopantsrepresented by A′ (e.g., A′₁, A′₂, . . . A′_(N)) and/or one or moredopants represented by B′ (e.g., B′₁, B′₂, . . . B′_(N)), as describedabove. As conventionally drawn, A-site cations occupy the corners, whileB-site cations sit in the body center of the perovskite structure 204A.Three oxygen atoms per unit cell rest on the faces of the perovskitestructure 204A. Various perovskite structures have, without limitation,a lattice constant close to approximately 4 Å due to the rigidity of theoxygen octahedra network and the well-defined oxygen ionic radius of1.35 Å. Advantageously, many different cations can be substituted onboth the A and B sites as dopants to achieve the various advantageousproperties described herein while maintaining the overall crystalstructure. According to various embodiments, a dopant atom can occupy Aor B sites to form a substitutionally doped solid solutions. It will beappreciated that a dopant occupying the A sites can have very differenteffect on the base polar material than a dopant occupying the B sites.

Still referring to FIG. 2A. in an illustrative example of a polar layercomprising barium titanate (BaTiO₃), which may be a paraelectricmaterial having a cubic perovskite structure, the A sites are occupiedby Ba atoms while Ti atoms occupy the B sites and are surrounded byoctahedra of 0 atoms, and the O atoms are located at the center of eachface of the unit cell. Above a Curie temperature, which may be about130° C. for BaTiO₃, in the paraelectric phase, the perovskite structure204A may be cubic or tetragonal. In the paraelectric phase, the O atomsmay occupy a mid-position with respect to each pair of 0 atoms onopposing faces of the unit cell. Below the Curie temperature, in theferroelectric phase, the perovskite structure 204A may have a tetragonalstructure in which the B sublattice (e.g., Ti sublattice in BaTiO₃) andO atoms may shift in opposite direction with respect to the Ba atoms,taken as reference. These atomic shifts may be accompanied with a smallrelaxation of the unit cell that becomes tetragonal (when theparaelectric phase is cubic) or further elongated tetragonal (when theparaelectric phase is tetragonal) and produce a stable polarization(e.g., about 26 μC/cm²). In the tetragonal phase, the cubic symmetry isbroken, resulting in six symmetry equivalent variants with polarizationalong the [100], [010] and [001] directions.

Referring to FIG. 2B, according to some embodiments, the crystallinepolar layer has a hexagonal crystal structure 204B-1/204-B-2. Thehexagonal crystal structure 204-B1 represents a side view, while thehexagonal crystal structure 204-B2 represents a top view. The hexagonalcrystal structure 204B-1/204-B-2 represents a crystalline oxide in aferroelectric state, and can be represented by a chemical formula RMnO₃,where R represents a metal cation, Mn represents a manganese cation andO represents an oxygen anion. In these embodiments, the crystallinepolar layer can have more than one element represented by R (e.g., A₁,A₂, . . . A_(N)) occupying interchangeable atomic positions and/or morethan one element in addition to Mn (e.g., B₁, B₂, . . . B_(N)) occupyinginterchangeable atomic positions, and can be doped with one or moredopants represented by A′ (e.g., A′₁, A′₂, . . . A′_(N)) and/or one ormore dopants represented by B′ (e.g., B′₁, B′₂, . . . B′_(N)), asdescribed above. In some embodiments, R is an element selected from thegroup consisting of cerium (Ce), dysprosium (Dy), erbium (Er), europium(Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu),neodymium (Nd), praseodymium (Pr), promethium (Pm), samarium (Sm),scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb), and yttrium(Y). The hexagonal crystal structure 204B-1 shows two layers of MnO₅trigonal bipyramids and two layers of R³⁺ ions. The crystalline polarlayer having the hexagonal crystal structure according to embodimentscan have a relatively large remnant polarization and relative high T_(C)in the range between 600 and 1000 K. The crystalline polar layers havingthe illustrated hexagonal structure includes close-packed layers of MnO₅bipyramids, which share corners in the ab planes (x-y plane in FIG. 2B).Along the hexagonal c axis (z direction in FIG. 2B), the layers of MnO₅are well separated by the R³⁺ ions. A cooperative tilting of thebipyramidal sites below the T_(C) displaces the R³⁺ ions along the caxis into two nonequivalent sites. Two of the R³⁺ ions within the unitcell move up (down), and one down (up), producing a ferroelectric state.The oxygen ions are also displaced in the ab plane. Both displacementsof R³⁺ ions and oxygen ions contribute to the ferroelectricpolarization, as illustrated in the pyramid structure 204B-3.

Referring to FIG. 2C, according to some embodiments, the crystallinepolar layer has a superlattice structure 204C-1. The illustratedsuperlattice structure 204C-1 represents a crystalline oxide in aparaelectric state, which may have a chemical formula ABO₃, where eachof A and B represents two or more metal cations and O represents anoxygen anion. For example, A may represent A₁, A₂, . . . A_(N), and/or Bmay represent B₁, B₂, . . . B_(N), and the polar layer can be doped withone or more dopants represented by A′ (e.g., A′₁, A′₂, . . . A′_(N))and/or one or more dopants represented by B′ (e.g., B′₁, B′₂, . . .B′_(N)), as described above.

In various embodiments, the superlattice structures can include one ormore A₁B₁O₃ layers that alternate with one or more A₂B₂O₃ layers, andcan be represented as a superlattice structure [A₁B₁O₃/A₂B₂O₃]_(n),where n is the number of alternating pairs of layers that can be 1 to100. The superlattice structures may be ordered compounds where each ofA₁B₁O₃ layers and A₂B₂O₃ layers can have two or more atomic monolayersbut as few as two atomic monoloayers. In the illustrated embodiment, aunit cell may be defined by five parallel planes defined by x or [100]and y or [010] directions. In the illustrated embodiment, B₁ and B₂ aresame and the unit cell has an upper half represented by the formulaA₁BO₃ and a lower half represented by the formula A₂BO₃ in the z or[001] direction, where each half can be analogized to a perovskitestructure 204A, with respect to the atomic positions, described abovewith respect to FIG. 2A. In the upper half of the unit cell, a firstcation A₁ occupies the corners intersected by an upper face, while asecond cation A₂ occupies the corners intersected by a lower face.B-site cations sit in the body center and three oxygen atoms per unitcell rest on the faces, in a similar manner as the perovskite structure204A described above with respect to FIG. 2A. The lower half of the unitcell is a mirror image of the upper half with a symmetry plane being thelower face of the upper half, such that the upper face of the lower halfis defined by the lower face of the upper half. Thus, in the lower halfof the unit cell, the second cation A₂ occupies the corners intersectedby an upper face, while the first cation A₁ occupies the cornersintersected by a lower face. B-site cations sit in the body center andthree oxygen atoms per unit cell rest on the faces, in a similar manneras the perovskite structure 204A described above with respect to FIG.2A. Thus, in the [001] direction, A₁/O planes having the A₁ cations andthe O anions alternate with A₂/O planes having A₂ cations and O anions,where a plane having the B cations and the O anions is interposedbetween each pair of alternating A₁/O and A₂/O planes, thereby forming aA₁BO₃/A₂BO₃ superlattice formed at an atomic layer level by alternatingA₁BO₃ layers and A₂BO₃ layers. The arrows indicate various atomicmotions associated with different energy lowering distortions in theA₁BO₃/A₂BO₃ superlattice. In the superlattice structure 204C-1, up anddown arrows indicated on the A₁ and A₂ cations, B cations and O anionsindicate directions of atomic displacements that an occur in somesuperlattice structures in response to an electric field when the polarlayer undergoes a ferroelectric phase transition, thereby giving rise toa polarization (Ps). In the superlattice structures 204C-2 and 240C-3,rotations of oxygen atoms in the indicated directions to give rise toalternative polarization states are illustrated, depending on thematerial.

In various embodiments, one of the alternating layers of thesuperlattice structure comprising SrTiO₃ layers, and the other of thealternating oxide layers are represented by A₂TiO₃ or A₂B₂O₃. Stillreferring to FIG. 2C, the illustrative example of a polar layer having asuperlattice structure comprises an ordered alloy comprising asuperlattice including first layers comprising SrTiO₃ alternating withsecond layers comprising PbTiO₃. In this example, referring to FIG. 2C,A₁ cations, A₂ cations, and B cations represent Pb cations, Sr cationsand Ti cations, respectively, such that the superlattice structurecomprises SrTiO₃ layers (e.g., lower half of the unit cell in FIG. 2C)alternating with PbTiO₃ (e.g., upper half of the unit cell in FIG. 2C)represented by [SrTiO₃/PbTiO₃]_(n). In some embodiments, thesuperlattice structure comprises SrTiO₃ layers alternating with LaAlO₃represented by [SrTiO₃/LaAlO₃]_(n).

In some embodiments, the polar layer comprises a ferroelectric oxideselected from the group consisting of BaTiO₃, PbTiO₃, KNbO₃, NaTaO₃,BiFeO₃ and PbZrTiO₃.

In some embodiments, the polar layer comprises a ferroelectric oxideselected from the group consisting of Pb(Mg,Nb)O₃, Pb(Mg,Nb)O₃—PbTiO₃,PbLaZrTiO₃, Pb(Sc,Nb)O₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃ and BaTiO₃—BaSrTiO₃.

In some embodiments, the polar layer comprises a ferroelectric oxideselected from the group consisting of LiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO,BaNaNbO, KNaSrBaNbO.

In some embodiments, the base ferroelectric material has a hexagonalcrystal structure, wherein the base ferroelectric material comprisesLuFeO₃ or has a chemical formula represented by RMnO₃, and wherein R isa rare earth element.

In some embodiments, the polar layer comprises Pb(Ti_(1-y)Zr_(y))O₃ orPb(Ti_(1-y-z)Zr_(y)Nb_(z))O₃, wherein each of y and z is greater thanzero.

In some embodiments, the polar layer comprises one of(Bi_(1-x)La_(x))FeO₃, (Bi_(1-x)Ce_(x))FeO₃ and BiFe_(1-y)Co_(y)O₃.

Conductive Oxide Electrodes Integrated with Storage Layer

The choice of materials for integrating various polar layers describedherein with oxide electrodes to form capacitors, and their depositionprocesses, can depend on a variety of factors, including the devicearchitecture, thermal budget, performance, reliability, difficulty ofintegration, environmental issues, cost, and other materials of thecapacitor. Integration of the polar layers between top and bottomelectrodes to form capacitors for memory devices disclosed herein facesmany challenges. For example, some polar layers such as ferroelectricoxides are deposited in an oxygen-containing atmosphere at relativelyhigh temperatures (e.g., 300° C.-800° C.), and at least one of theelectrodes (e.g., the bottom electrode on which the polar layer isformed) should be resistant to oxidation under these conditions and beable to withstand the processing conditions of the polar oxide. For thisreason, some polar layers in the industry have been integrated withoxidation-resistant noble metals, such as Pt and Pd. However, becausenoble metals are difficult to etch and have poor adhesion, theirintegration has been limited in the industry. Furthermore, noble metalscan form deep levels in the underlying Si substrate when diffusedtherein and severely degrade transistor performance. In addition, someelectrodes can detrimentally influence the ferroelectric properties ofthe polar layer, e.g., reduce the remnant polarization.

In addition, the inventors have discovered that, by engineering thematerial composition and the crystal structure of the upper and lowerelectrodes comprising conductive oxides according to embodimentsdescribed herein, various ferroelectric characteristics of theferroelectric capacitor may be maintained or improved, including theswitching voltage, switching time, remnant polarization, saturationpolarization, coercive field, ferroelectric transition temperature,electrical conductivity of the electrodes and leakage current, to name afew. For example, as described above, conventional ferroelectriccapacitors, e.g., those including Pt electrodes, can give rise to aninterfacial layer between the polar layer and the electrode(s), whichcan lead to charge injection and screening effects, thereby increasingthe effective coercive field of the polar layer. Unlike the conventionalferroelectric stacks, the engineered electrodes according to embodimentsdescribed herein can reduce or eliminate these effects. Furthermore, theupper and lower electrodes comprising conductive oxides according toembodiments described herein can serve as a diffusion barrier and enablethe integration of various polar layers described above without usingnoble metals such as Pt or Pd that are difficult to integrate.

To address these and other objectives, according to various embodiments,a capacitor stack comprises first and second crystalline conductive orsemiconductive oxide electrodes on opposing sides of a polar layer,wherein the polar layer can be any of the polar layers disclosed herein.In various embodiments, the polar layer comprises any crystalline basepolar material doped with a dopant as described herein. The base polarmaterial includes one or more metal elements and one or both of oxygenor nitrogen, wherein the dopant comprises a metal element that isdifferent from the one or more metal elements and is present at aconcentration such that a remnant polarization of the polar layer isdifferent than that of the base polar material without the dopant bymore than about 5 μC/cm². The capacitor stack additionally comprisesfirst and second crystalline conductive or semiconductive oxideelectrodes on opposing sides of the polar layer, wherein the polar layerhas a lattice constant that is matched within about 20% of a latticeconstant of one or both of the first and second crystalline conductiveor semiconductive oxide electrodes. In some other embodiments, asemiconductor device comprises a capacitor stack, which in turncomprises a crystalline polar layer comprising a base polar materialsubstitutionally doped with a dopant. The base polar material comprisesa metal oxide having one of a perovskite structure, a hexagonal crystalstructure or a superlattice structure. The dopant comprises a metal ofone of 4d series, 5d series, 4f series or 5f series that is differentfrom metal(s) of the metal oxide. The capacitor stack further comprisesfirst and second crystalline conductive or semiconductive oxideelectrodes on opposing sides of the crystalline polar layer, wherein thecrystalline polar layer has the same crystal structure as one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes. An example capacitor stack that can achieve these desirableeffects is illustrated with respect to FIG. 3.

FIG. 3 schematically illustrates crystal structures of the layers of acapacitor stack 312 comprising first (lower) and second (upper)conductive or semiconductive oxide electrodes 304, 300 and a polar layer308 interposed therebetween and having a matching crystal structure,according to some embodiments. In the illustrated embodiment, thematching crystal structure is a perovskite structure, as described abovewith respect to FIG. 2A. In this embodiment, the polar layer 308comprises a ferroelectric oxide having a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein A and A′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein B and B′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein one or both of the A′ and the B′are dopants, wherein m, n and z are integers, and wherein one or both ofx and y are greater than zero. As described above, A can represent oneor more alloying elements that form a solid solution, A can representone or more alloying elements that form a solid solution and each of A′and B′ can represent one or more dopants. One or both of the first andsecond conductive or semiconductive oxide electrodes 304, 300 comprisean oxide having a chemical formula represented byC_((p-u))C′_(u)D_((q-v))D′_(v)Ow, wherein C and C′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein D and D′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein p, q and w are integers, andwherein one or both of u and v are greater than zero. Additionalelements (e.g., C″, C′″, etc.) can occupy interchangeable atomicpositions with C and C′, and additional elements (e.g., D″, D′″, etc.)can occupy interchangeable atomic positions with D and D′ to form solidsolutions. The different elements and their atomic fractions can betuned to tune the lattice constant to more closely match that of thepolar layer 308, and/or to tune the resistivity, among other parameters.

In various embodiments disclosed herein, the compositions of the polarlayer 308 and the first and second conductive or semiconductive oxideelectrodes 304, 300 can be tuned such that the polar layer 308 has alattice constant that is matched within about 25%, 20%, 15%, 10%, 5%,2%, 1%, 0.5%, 0.2%, 0.1%, or a percentage in a range defined by any ofthese values, of a lattice constant of one or both of the first andsecond conductive or semiconductive oxide electrodes 304, 300 that arecontacting the polar layer 308.

At least portions of the polar layer 308 and one or both of the firstand second conductive or semiconductive oxide electrodes 304, 300 may bepseudomorphic or pseudomorphically strained. For example, according toembodiments, the polar layer 308 has a region having a lateral dimensionbetween about 10 nm and 500 nm that is pseudomorphic with the first andsecond conductive or semiconductive oxide electrodes 304, 300. Thepseudomorphic region can correspond to, e.g., a grain of the polar layer308. Without being bound to any theory, a person having ordinary skillin the art would appreciate that whether or not pseudomorphicity isachieved depends on, among other factors, the thickness of the layersand the lattice mismatch, where at least partial pseudomorphicity can beachieved so long as the strain energy is below a critical energy forformation of misfit dislocation. The inventors have realized that therelatively low lattice mismatch and at least partial pseudomorphicformation of the layers can reduce contact resistance, therebycontributing to enablement for low voltage switching (e.g., <1200 meV)of a ferroelectric capacitor, as described herein. In addition, byengineering the material composition and the crystal structure of alower electrode on which the crystalline polar layer is formed, at leasta portion of the crystalline polar layer such as one or more grains maybe epitaxially grown, such that the in-plane lattice constant and/orcrystal symmetry of the lower electrode may be imposed on thecrystalline polar layer formed thereon. Without being bound to anytheory, the epitaxial strain resulting from the lattice mismatch betweenthe polar layer and the first and/or second crystalline conductive orsemiconductive oxide electrodes can strongly couple with the polarlayer. Under some circumstances, new phase(s), not present in the bulkphase diagram of the polar layer can be epitaxially stabilized,strain-engineering may be possible to tune specific ferroelectricproperties to desired values, and/or misfit dislocations may partly orfully relieve the strain to tune the ferroelectric properties.

Thus, to derive these and other benefits, according to variousembodiments described herein, one or both of the first and secondconductive or semiconductive oxide electrodes 304, 300 have a thicknessbetween about 0.5 and 5 nm, 5 and 10 nm, 10 and 15 nm, 15 and 20 nm, 20and 25 nm, 25 and 30 nm, 30 and 35 nm, 35 and 40 nm, 40 and 45 nm, 45and 50 nm, or a thickness in a range defined by and inclusive of any ofthese values. Furthermore, the thickness may also be optimized to reducethe series voltage added to the switching voltage by the bulk resistanceof the electrodes.

In some embodiments in which the polar layer 308 has a perovskitestructure as disclosed above, one or both of the first and secondconductive or semiconductive oxide electrodes 304, 300 comprise an oxideselected from the group consisting of (La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃,YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃, SrRuO₃, LaMnO₃, SrMnO₃, LaCoO₃ SrCoO₃or IrO₃.

In some embodiments, a thin layer (e.g., 5 nm-15 nm) of one or both ofthe first and second conductive or semiconductive oxide electrodes 304,300 having a perovskite structure may serve as a template on which thepolar layer 308 having a perovskite structure is formed or grown toachieve various advantages including strain engineering, low contactresistance and preservation or enhancement of ferroelectric propertiesof the polar layer 308, as described above. However, further improvementin the overall performance of the electrodes may be achieved by forminga stack with a further electrode. For example, the further electrode mayprovide higher electrical conductivity, such that a first electrodestack including the first conductive or semiconductive oxide electrode304 and a first further electrode formed thereon may provide a loweroverall electrical resistivity relative to the first conductive orsemiconductive oxide electrode 304 having a comparable or the samethickness. Similarly, a second electrode stack including the secondconductive or semiconductive oxide electrode 300 and a second furtherelectrode formed thereon may provide a lower overall electricalresistivity relative to the second conductive or semiconductive oxideelectrode 300 having a comparable or the same thickness. Furthermore,the further electrode may serve as a diffusion barrier, e.g., for oxygendiffusion. The inventors have discovered that these and other advantagescan be achieved using a further electrode comprising a conductive binaryoxide. In these embodiments, the polar layer 308 directly contacts oneor both of the first and second conductive or semiconductive oxideelectrodes 304, 300, and the capacitor further comprises a furtherelectrode formed on one or both of first and second conductive orsemiconductive oxide electrodes 304, 300, wherein the further electrodecomprises a conductive binary metallic oxide selected from the groupconsisting of an iridium (Ir) oxide, a ruthenium (Ru) oxide, a telluriumoxide, a palladium (Pd) oxide, an osmium (Os) oxide or a rhenium (Re)oxide. While the binary oxides have a non-perovskite structure, theyprovide higher conductivity, and a conductive or semiconductive oxideelectrode having a perovskite structure formed thereon can provide aseed or a template for the growth, e.g., epitaxial growth, of the polarlayer 308 having a perovskite structure at relatively low temperatures.

As described herein, one or both of the first and second conductive orsemiconductive oxide electrodes 304, 300, or one or both of the firstand second electrode stacks comprising the first and second conductiveor semiconductive oxide electrodes 304, 300, respectively, havesufficiently high electrical conductivity such that they can serve as aconductive electrode suitable for low voltage switching, e.g., <1200meV. Accordingly, in various embodiments, one or both of the first andsecond conductive or semiconductive oxide electrodes 304, 300 or one orboth of the first and second electrode stacks comprising the first andsecond conductive or semiconductive oxide electrodes 304, 300,respectively, have a resistivity lower than about 0.1, 0.05, 0.02, 0.01,0.005, 0.002, 0.001, 0.0005 Ohms-cm, or a resistivity in a range definedby any of these values.

While in the above description with respect to FIG. 3, the illustratedexample of a matching crystal structure between the polar layer 308 andone or both of the first and second conductive or semiconductive oxideelectrodes 304, 300, is a perovskite structure, embodiments are not solimited, and it will be appreciated that the various materials and stackcombinations described herein for the first and second conductive orsemiconductive oxide electrodes 304, 300 having a perovskite structurecan be integrated with a polar layer 308 having a superlattice structuredescribed above with respect to FIG. 2C, according to some otherembodiments.

In yet some other embodiments, the matching crystal structure betweenthe polar layer 308 and one or both of the first and second conductiveor semiconductive oxide electrodes 304, 300 may be a hexagonal structureas described above with respect to FIG. 2B.

In yet some other embodiments, the crystal structure of one or both ofthe first and second conductive or semiconductive oxide electrodes 304,300 may be a delaffosite structure, a spinel structure or a cubicstructure. In these embodiments, one or both of the first and secondconductive or semiconductive oxide electrodes 304, 300 may comprise oneor more of PtCoO₂ and PdCoO₂, Al-doped ZnO and other conductive oxideshaving a delafossite structure that can be integrated with polar layershaving a hexagonal crystal structure; and Fe₃O₄, LiV₂O₄ and other oxideshaving a spinel structure and/or Sn-doped In₂O₃ having a cubic structurethat can be integrated with polar layers having a perovskite orsuperlattice structure, among others.

Polar Layer Design for Low Voltage Switching and Nonvolatility ofFerroelectric Capacitors by Doping a Base Polar Material

As discussed above, a ferroelectric capacitor for a semiconductordevice, e.g., FeRAM device, in which the polar layer has a relativelyhigh remnant polarization while having a relatively low ferroelectrictransition voltage for ultra-low voltage applications has been difficultto achieve. In addition, designing the polar layer for nonvolatilememory applications, e.g., such that data can be read after at least 10years at room temperature, has faced even greater challenge. To addressthese and other needs, in the following, a design approaches for aferroelectric capacitor, e.g., for an FeRAM, that is capable of beingswitched at ultra-low voltages (e.g., <1200 mV) while simultaneouslydisplaying relatively high remnant polarization (e.g., >10 μC/cm²) fornonvolatile memory applications, is disclosed. According to variousembodiments, a capacitor comprises a polar layer comprising acrystalline base polar material doped with a dopant as described herein.The base polar material includes one or more metal elements and one orboth of oxygen or nitrogen, wherein the dopant comprises a metal elementthat is different from the one or more metal elements and is present ata concentration such that a ferroelectric switching voltage of thecapacitor or the polar layer is different than that of the base polarmaterial without the dopant by more than about 100 mV, and/or that aremnant polarization of the polar layer is different than that of thebase polar material without the dopant by more than about 5 μC/cm². Thecapacitor stack additionally comprises first and second crystallineconductive or semiconductive oxide electrodes on opposing sides of thepolar layer, wherein the polar layer has a lattice constant that ismatched within about 20% of a lattice constant of one or both of thefirst and second crystalline conductive or semiconductive oxideelectrodes

Using the design approach described herein, a capacitor or the storagelayer 104 (FIG. 1A) included therein has a switching voltage that islower than about 1200 mV, 1100 mV, 1000 mV, 900 mV. 800 mV, 700 mV, 600mV, 500 mV, 400 mV, 300 mV, 200 mV, 100 mV, or a voltage in rangedefined by any of these values below the ferroelectric transitiontemperature. In addition, the storage layer 104 (FIG. 1A) can have aremnant polarization of 5-30 μC/cm², 30-50 μC/cm², 50-70 μC/cm², 70-90μC/cm², 90-110 μC/cm², 110-130 μC/cm², 130-150 μC/cm2, or a value in arange defined by any of these values.

FIG. 4A schematically illustrates a polarization-field (P-E) loop 400Aassociated with a hysteresis caused by a potential barrier between twowells of a double well curve corresponding to switching by ferroelectrictransitions between stable remnant polarization states, and theassociated atomic displacements. As described above with respect toFIGS. 2A and 1B, the P-E loop 400A is characterized by, starting with apolarization P=0 at which the polar layer is in a paraelectric phasehaving the paraelectric perovskite structure 204A (FIG. 2A), anincreasing polarization with increasing field until it reachessaturation at +Pmax. After the saturation is reached at +Pmax, when theelectric field is subsequently reduced, at E=0, a remnant polarization+Pr remains, and the polar layer is in a first ferroelectric phase.Below the Curie temperature, in the first ferroelectric phase, theperovskite structure 204A-1 may have a tetragonal structure in which theB sublattice and O atoms may shift in opposite direction with respect tothe A atoms, taken as reference. Upon application of an increasingnegative electric field until reaching saturation at −Pmax, andsubsequently reducing the electric field back to E=0, a remnantpolarization −Pr remains, and the polar layer is in a secondferroelectric phase. Below the Curie temperature, in the secondferroelectric phase, the perovskite structure 204A-2 may have atetragonal structure in which the B sublattice and O atoms may shift inopposite directions with respect to the A atoms, taken as reference, andin opposite respective directions with respect to the firstferroelectric phase.

FIG. 4B illustrates a schematic free energy curve 400B exhibiting adouble well potential corresponding to switching by ferromagnetictransitions between remnant polarization states and the associatedatomic displacements for a ferroelectric layer having a perovskitecrystal structure. For illustrative purposes only and without limitationto the crystal structure of the polar layer, the ferroelectric switchingphenomenon in a polar layer is described herein with respect to a polarlayer having a perovskite structure. As illustrated, two local minima inthe double well potential free energy curve 400B represent first andsecond ferroelectric states having remnant polarizations +Pr and −Pr,represented by the tetragonal perovskite structures 204A-1 and 204A-2,respectively. The two ferroelectric states are separated by a doublewell energy barrier ΔE. The inventors have recognized that, by loweringthis energy barrier of the free energy curve while maintaining arelatively large polarization values, the ferroelectric capacitorshaving ultra-low transition voltages and nonvolatile memory states canbe obtained.

FIG. 4C is a graph 400C showing calculations of the double wellpotential of the free energy curve of a ferroelectric oxide layer formedby doping a base ferroelectric oxide layer with varying amounts of adopant, thereby tuning the energy barrier between stable remnantpolarization states, for achieving an ultra-low transition ferroelectrictransition voltage, according to embodiments. In the illustratedexample, the base ferroelectric oxide used for the calculation isPbZrTiO₃, and the dopant is La substitutionally interchangeablyoccupying A sites of the perovskite structure, such that the polar layercomprises PbLaZrTiO₃. In the illustrated example, the base ferroelectricoxide has a starting remnant polarization of about 90 μC/cm² and astarting double well potential of about 290 meV. Upon adding up to 25%of La, the double well energy barrier has reduced by about 100 meV toabout 190 meV, accompanied by a reduction in remnant polarization byabout 15 μC/cm². The example calculation demonstrates compositions thatsatisfy a polar layer suitable for nonvolatile memory, which is capableof being switched at ultra-low voltages as low as about 200 mV, whilesimultaneously displaying relatively high remnant polarization of about75 μC/cm² for nonvolatility.

The inventors have discovered that the approach in the illustratedexample can be generalized to various base polar material and dopantsdescribed herein, depending on the application-dependent parameters,e.g., the transition (e.g., switching) voltage and/or remnantpolarization. According to embodiments, the starting base ferroelectricoxide has a relatively high remnant polarization, e.g., to account forreduction in the same with doping, as illustrated with respect to FIG.4C, and for the desired level of nonvolatility. According toembodiments, when the base polar material is a base ferroelectricmaterial, the composition of the base ferroelectric material is selectedor tuned such that the remnant polarization of the base ferroelectricmaterial and the remnant polarization of the doped polar material isabout 5-30 μC/cm², 30-50 μC/cm², 50-70 μC/cm², 70-90 μC/cm², 90-110μC/cm², 110-130 μC/cm², 130-150 μC/cm², or a value in a range defined byany of these values. Depending on the application, when the base polarmaterial is a base ferroelectric material, the composition of the baseferroelectric material is selected or tuned such that the double wellenergy barrier of the base ferroelectric material and the double wellbarrier of the doped polar material is 200-300 meV, 300-400 meV, 400-500meV, 500-600 meV, 600-700 meV, 700-800 meV, 900-1000 meV, or a value ina range defined by any of these values. To the starting baseferroelectric material having relatively high remnant polarization andrelatively high double well energy barrier, a dopant as described hereinis added. The added dopant can lower the double well energy barrier by0-100 meV, 100-200 meV, 200-300 meV, 300-400 meV, 400-500 meV, or avalue in a range defined by any of these values. The added dopant canlower the remnant polarization by about 5%, 10%, 20%, 30%, 40%, 50%,60%, 70%, or a value in a range defined by any of these values.

The inventors have discovered that the double well potential tuningapproach can also enable tuning the ferroelectric capacitor for highdata retention performance. After establishing a remnant polarization,the ferroelectric state cannot ideally retain its remnant polarizationindefinitely because of various effects that can cause backswitching.The polarization slightly decreases with time, which may be referred toas retention loss, which is characterized by the difference betweenswitching and non-switching charge becoming smaller over time. Theretention loss is observed as a long-term relaxation of the remnantpolarization of the hysteresis, which can be determined by measuring theretained charge, e.g. by means of a read pulse, after a certain periodof time when the state was stored by a write pulse.

For many nonvolatile memory applications, the ferroelectric capacitorshould store the digital information longer than 10 years, e.g., atleast at room temperature. Without being bound to any theory, thepolarization may follows a logarithmic decay that begins at to with thedecay rate m, which can be expressed generally by an expression such as:

P(t)=P(t ₀)−m log(t/t ₀),

where:

m∝exp(−W/kT),

where W is an activation energy and k is the Boltzmann constant, whichcan be related to the double well potential described above. When theremnant polarization falls below a critical threshold value Pc att=t_(C), a sense amplifier may no longer be able to distinguish betweenthe memory states. The retention loss can be analyzed statisticallyusing an expression such as:

log log(t _(C) /t ₀)∝(W/kT).

The inventors have discovered that, when the double well potential andthe remnant polarization of a ferroelectric capacitor is according tovarious embodiments disclosed herein, the retention loss may not cause adata retention failure after at least 10 years at a temperature at orexceeding room temperature.

FIG. 5 schematically illustrates, without being bound to any theory,energy considerations of switching and nonvolatile storage insemiconductor devices comprising a ferroelectric capacitor, according toembodiments. The inventors have discovered that, as described above, theenergy barrier for data retention loss can be associated with, e.g.,proportional to, the double well potential of the free energy curvedescribed above with respect to FIGS. 4A-4C. Without being bound to anytheory, the energy barrier E(P) for data retention can be related anorder parameter P as expressed by Ginzburg-Landau theory as:

F(P,T)=g ₂ P ²/2+g ₄ P ⁴/4+g ₆ P ⁶/6−PE/2

where g₂, g₄ and g₆ are coefficients and PE is potential energy. Theminima of first and second derivatives of F(P,T) define the phasetransitions. Advantageously, based on double well potential barriersdescribed above for ferroelectric capacitors according to embodiments, aratio (X) of switching energy E_(SWITCH) and the energy barrier forretention for memory devices can be on the order of unity. Similar ratiofor some other memory technologies can be much higher, e.g., two ordersof magnitude higher, for some spin torque transfer memory technologies.

Dopant Engineering for Polar Layers for Ferroelectric Capacitors

As described above, in various embodiments, to achieve a ferroelectriccapacitor according to embodiments for a semiconductor device, e.g.,FeRAM device, in which the ferroelectric oxide layer has a relativelyhigh remnant polarization while having a relatively low ferroelectrictransition voltage, a ferroelectric capacitor is formed by doping a basepolar material having a relatively high remnant polarization to tune,e.g., lower the double well energy barrier of the free energy curve(e.g., FIG. 4B). In the following, engineering the dopants to achievethese and other objectives are described.

As described above, the polar layer comprises a ferroelectric oxidehaving a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein m, n and z are integers,and wherein one or both of x and y are greater than zero. A and A′ aremetals that occupy interchangeable atomic positions in the crystalstructure and B and B′ are metals that occupy interchangeable atomicpositions in the crystal structure. One or both of the A′ and the B′ maybe dopants. As described above, an A′ ion can have a different oxidationstate relative to the A ion it replaces, and/or B′ ion can have adifferent oxidation state relative to the B ion it replaces. Thus, inthese embodiments, the ferroelectric oxide comprises a base polarmaterial, which may be represented by a base chemical formulaA_(m)B_(n)O_(z), that is doped with one or more dopants A′ and/or B′ tohave the chemical formula A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z). In thefollowing, engineering of dopants A′ and B′ that occupy different atomicsites within the crystal structure and their advantageous effects aredescribed. In FIG. 6, dopants corresponding to A′ are described, and inFIG. 7, dopants corresponding to B′ are described.

FIG. 6 illustrates a schematic perovskite crystal structure 600 of apolar layer doped with a dopant A′ 600 that can replace atoms of themetal A occupying corner positions in a base polar material having achemical formula ABO₃, according to embodiments. For illustrativepurposes, dopant engineering is described for a polar layer having aperovskite structure. However, the inventive concepts described hereincan apply in a similar manner to polar layers having other crystalstructures including hexagonal crystal structures and superlatticestructures.

As described above, the A′ dopants occupy corner positions of a unitcell of a perovskite structure. A′ can have a different oxidation stateas the A atom it replaces. A′ dopants and their concentration can beselected to tune, among other parameters and without limitation,switching parameters such as the switching voltage and/or remnantpolarization. Without being bound to any theory, the switchingparameters can be tuned by, e.g., tailoring the double well potential ofthe free energy curve as discussed above (e.g., FIG. 4B). In polarlayers having a superlattice structure as described above with respectto FIG. 2C, the switching parameters can be tuned by varying the mode ordegree of atomic motions associated with polarization, as describedabove with respect to FIG. 2C. The A′ dopants can be selected, amongother factors, based the capability of being substitutionally replacethe A atoms, e.g., while having a different oxidation state than the Aatoms, which in turn can depend on valency and atomic radii, among otherfactors, and a difference in the atomic polarizability (a) of A′ dopantsrelative to the A atoms in the crystal structure. In variousembodiments, the a of the A′ dopant may be about 2%, 5%, 10%, 20%, 50%,100%, 200%, 500%, 1000%, 2000% or a percentage in a range defined by anyof these values, relative to the a of the A atom for tuning theswitching voltage.

According to various embodiments, A′ can be a metal of one of 4d series,5d series, 4f series or 5f series. For example, the A′ can be alanthanide element, such as La of 4f series in the illustrated exampleimplementation in FIG. 4C, or Nb in the 4d or 5d series.

According to embodiments, the amount of A′ can be 0.1-5 atomic %, 5-10atomic %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic % or an atomic %in a range defined by any of these values, for instance between 0.1-20atomic %.

FIG. 7 illustrates a schematic perovskite crystal structure of polarlayer doped with a dopant B′ that can replace atoms of the metal Boccupying the center position in a base polar material having a chemicalformula ABO₃, according to embodiments. As described above, the B′dopants occupy center positions of a unit cell of a perovskitestructure. B′ dopants and their concentration can be selected to tune,among other parameters and without limitation, charge transfercharacteristics, such as leakage current. The B′ dopants can beselected, among other factors, based the capability of beingsubstitutionally replace the B atoms, e.g., while having a differentoxidation states than the B atoms, which in turn can depend on valencyand atomic radii, among other factors. The inventors have discoveredthat transition metal of 3d series can be particularly advantageousreducing charge transfer under field in the polar layer.

According to embodiments, the B′ is transition metal element having arelatively low atomic number. For example, B′ can be an element selectedfrom the group consisting of Mn, Sc, Ti, V, Cr, Co, Ni, Cu, Zn or other4d series metals.

According to embodiments, the amount of B′ can be 0.1-5 atomic %, 5-10atomic %, 10-15 atomic %, 15-20 atomic %, 20-25 atomic % or an atomic %in a range defined by any of these values, for instance between 0.1-20atomic %.

Diffusion Barriers

As described above, various layers of ferroelectric capacitors describedherein comprise various chemical elements at specific concentrations,which in turn can be important for device characteristics such as lowvoltage operation and high remnant polarization. To maintain the devicecharacteristics through fabrication and post fabrication usage, thechemical compositions and interfaces of the layers of the ferroelectriccapacitors should be maintained through different processing steps. Inaddition, some elements in the ferroelectric capacitors can adverselyaffect other circuitry of the integrated circuit. In particular, theferroelectric capacitors according to some embodiments are formed aspart of the back end of the line (BEOL), after CMOS devices such astransistors are formed in the front end of the line (FEOL). As a result,diffusion of chemical elements from the ferroelectric capacitor to thesurrounding features associated with the CMOS circuitry that can causevarious failures. Conversely, diffusion of chemical elements from theferroelectric capacitors to the surrounding features associated with theCMOS circuitry. For example, as described above with respect tointegration of electrodes, subsequent processes for fabrication, e.g.,for forming a polar layer comprising an oxide, may be under an oxidizingenvironment at relatively high temperatures (e.g., 500° C.-800° C.).Thus, a diffusion barrier layer may needed to suppress the diffusion ofoxygen from the ferroelectric capacitor region to the featuresassociated with the CMOS circuitry, For example, the ferroelectriccapacitor may be formed on a contact via or plug that electricallyconnects to a transistor, e.g., a drain of the transistor. The contactvia or plug may be formed of, e.g., polycrystalline Si, W or WSi_(x). Asa result, an oxygen barrier may serve to maintain the electrical contactbetween the transistor and the lower electrode of the ferroelectriccapacitor by suppressing the oxidation of the contact via and/or areaction between the lower electrode and the contact via. Furthermore,reactions between the barrier itself and either the contact via and thelower electrode have to be suppressed. To serve these and other needs,ferroelectric capacitors according to embodiments can include verticaldiffusion barriers.

FIGS. 8A, 8B and 8C schematically illustrates side views of capacitorstacks 800A, 800B and 800C, respectively, each comprising a storagelayer 804 interposed between first and second conductive oxide electrodelayers 808, 812, according to various embodiments. The storage layer804, the upper or a first conductive oxide electrode layer 808 and thelower or a second conductive oxide electrode layer 812 can be configuredaccording to various embodiments disclosed above, detailed descriptionsof which are omitted for brevity. The storage layer 804 comprises apolar layer comprising an oxide layer that is deposited under anoxidizing environment and/or relatively high temperatures as describedabove.

Referring to the capacitor stack 800B, in some embodiments, one or bothof the first and second conductive oxide electrode layers 808, 812 haveformed thereon a upper and lower barrier layers 816, 820, respectively,on opposite sides of the storage layer 804. In various embodiments, oneor both of the upper and lower barrier layers 816, 820 comprises aconductive barrier layer material such as a metal or an intermetalliccompound, e.g., a refractory metal or a refractory intermetalliccompound, that can suppress diffusion while providing high electricalconductivity.

In some embodiments, the upper and lower barrier layers 816, 820 includeone or more of a Ti—Al alloy, a Ni—Al alloy, a Ni—Ti alloy, a Ni—Gaalloy, a Ni—Mn—Ga alloy, a Fe—Ga alloy, a metal boride, a metal carbide,a metal nitride, Ta metal, W metal and Co metal.

In some embodiments, the upper and lower barrier layers 816, 820 includean intermetallic compound such as Ti₃Al, TiAl, TiAl₃, Ni₃Al, NiAl₃ NiAl,Ni₂MnGa, FeGa and Fe₃Ga. In some embodiments, the upper and lowerbarrier layers 816, 820 include IrOx, where x=0 to 2. Advantageously, asdescribed above, IrO_(x) may also serve the function of a furtherelectrode with low electrical resistance. Thus, these embodiments canreduce the number of layers over the ferroelectric capacitor stack.

As described above, to maintain the device characteristics throughfabrication and post fabrication usage, diffusion of atoms to and fromthe ferroelectric capacitor are suppressed using upper and lower barrierlayers 816, 820, according to embodiments. In addition to suppressingthe diffusion vertically, under similar integration schemes, horizontaldiffusion of atoms to and from the ferroelectric capacitor may also needto be suppressed. For example, horizontal diffusion barriers accordingto embodiments may serve, e.g., to suppress hydrogen diffusion. Hydrogenis used many semiconductor backend processes for passivation of surfacesand interfaces during the final forming gas (H2/N2) annealing. However,hydrogen can substantially damage or even destroy ferroelectricproperties of some ferroelectric capacitors. Thus, there is a need foreffective sidewall barrier layers to suppress exposure of one or morelayers of the ferroelectric capacitor to hydrogen during subsequentthermal steps.

Referring to the capacitor stack 800C, in some embodiments, thecapacitor stacks 800A or 800B may have formed thereon a barrier sealantlayer 824 on one or both side surfaces of one or more of the storagelayer 104, the first oxide electrode layer 808, the second conductiveoxide electrode layer 812, the upper barrier layer 816 and the lowerbarrier layer 820. Unlike the upper and lower barrier layers 816, 820,the barrier sealant layer(s) 824 is electrically insulating to preventan electrical short across the first and second oxide electrode layers808, 812. In some embodiments, the barrier sealant layer(s) 824comprises a metal oxide, e.g., a Mg-containing oxide or an Al-containingoxide. The metal oxide may include, e.g., one or more of MgO, TiAlO andLaAlO. In some embodiments, the barrier sealant layer(s) 824 is aconformally deposited layer and/or is formed as a spacer structure byisotropic etching after depositing.

Alternative barrier sealant layers 824 are possible. For example, insome embodiments, one or both of the barrier layers 824 comprisesidewalls of one or more of the first and second conductive oxideelectrode layers 808, 812 and the storage layer 804 that are formed byoxidation, fluorination and/or chlorination.

Alternative Polar Layers and Configurations

In the above, various compositions of the storage layer have beendescribed. Alternative arrangements are possible.

Some materials, referred to as paraelectric materials, display anonlinear polarization as a function of applied electric field, similarto ferroelectric materials described above. However, unlikeferroelectric materials, paraelectric materials do not display a remnantpolarization when the electric field is removed. In some embodiments, aparaelectric oxide layer is included in the capacitor stack in lieu ofor in addition to a ferroelectric oxide layer. The resulting capacitorcan be used, e.g., for volatile memory applications.

In these embodiments, a capacitor arranged similarly to the capacitors800A, 800B and 800C (FIGS. 8A-8C) comprises a crystalline polar layercomprising a base ferroelectric material substitutionally doped with adopant. The base ferroelectric material comprises one or more metalelements and one or both of oxygen or nitrogen. The dopant comprises ametal element different from the one or more metal elements, wherein thedopant is present at a concentration such that a remnant polarization ofthe base ferroelectric material initially greater than about 5 μC/cm² toabout zero. In some embodiments, a capacitor is arranged similarly tothe capacitors 800A, 800B and 800C (FIGS. 8A-8C), except that one ormore of the storage layer 804, the first conductive oxide electrodelayer 808 and second conductive oxide electrode layer 812 have anon-uniform composition, e.g., a graded composition that increases ordecreases in one or the other of vertical directions from any pointwithin the thickness.

Memory Cell Including Ferroelectric Capacitor

FIG. 9 illustrates a cross-sectional view of an example FeRAM cell 900that can be implemented with various capacitor configurations describedabove, according to embodiments. The FeRAM cell 900 includes an accessor a select metal oxide semiconductor (MOS) transistor including a gatedielectric 936 and a gate electrode 938 formed over a channel regionbetween a source 932 and a drain 934. Power or sensing circuitry (notshown) may be electrically connected to the source 932 and/or drain 934,and gated by the gate electrode 938. The transistor is covered with afirst-level dielectric layer 940, e.g., SiO₂. A drain contact 942, e.g.,a silicon plug, may be formed to contact the drain 934 to electricallyconnect the transistor to a ferroelectric capacitor.

A ferroelectric capacitor may be formed over the drain contact 942. Thecapacitor comprises a storage layer 804 interposed between a first/topelectrode (stack) 808A/808B and a second/bottom electrode (stack)812A/812B, according to various embodiments. As described above, one orboth of the first/top electrode layer 808A/808B and the second/bottomelectrode 812A/812B can include more than one layer. For example, thefirst electrode 808A/808B may include a first conductive oxide 808A,which can have a crystal structure matching that of the storage layer804, and a further electrode 808B comprising a binary conductive metaloxide. Similarly, the second electrode 812A/812B may include a secondconductive oxide 812A, which can have a crystal structure matching thatof the storage layer 804, and a further electrode 812B comprising abinary conductive metal oxide. The second electrode 812A/812B of theferroelectric capacitor is electrically connected to the drain 934 ofthe transistor through the drain contact 942.

Still referring to FIG. 9, as described above with respect to FIG. 8B, alower barrier layer 820 may be formed between the second electrode812A/812B to serve as a diffusion barrier to suppress undesirablediffusion therethrough to and from any of the layers of the capacitorthereover including, e.g., oxygen diffusion into the drain contact 942during the deposition and/or a post-anneal of the storage layer 804.Similarly, while not shown, an upper barrier layer may be formed on thefirst electrode 808A/808B to suppress diffusion therethrough. Thediffusion barrier layers can have any of the compositions andconfigurations described above, e.g., with respect to FIG. 8B.

Still referring to FIG. 9, the ferroelectric capacitor may further haveformed thereon one or more barrier sealant layer to suppress lateraldiffusion. For example, in FIG. 9, remaining portions 812 of asacrificial barrier layer are also shown. The sacrificial barrier may beformed as a blanket layer prior to depositing the storage layer 804, tosuppress diffusion of atoms to and from the storage layer 804 as it isbeing deposited, or during a post-deposition anneal. The sacrificialbarrier layer is subsequently removed to expose the underlying secondelectrode 812A/812B and to expose the first-level dielectric layer 940,thereby resulting in the illustrated remaining portions 812 of thesacrificial layer. The remaining portions 812 serve as a permanentbarrier sealant layer for suppressing lateral diffusion to and fromand/or through the second electrode 812A/812B. In addition, while notshown, a further a barrier sealant layer may be formed on one or bothsidewall surfaces of the ferroelectric capacitor to cover sidesurface(s) of the storage layer 804 and/or the first electrode 808A.Each of the barrier sealant layers can have any of the compositions andconfigurations described above, e.g., with respect to FIG. 8C.

While not shown, a plurality transistors and capacitors may beconfigured to form a memory array. Each of the transistor gates 938,sources 932 and the top electrode 808A/808B of the capacitors may beindividually contacted and separately controlled through metallizationlevels (not shown) to enable writing, non-volatile storage, and readingof the ferroelectric memory cell.

In operation, writing in the FeRAM cell 900 may be accomplished byapplying a field across the storage layer 804 of the cell capacitor,thereby inducing a ferroelectric transition as described above withrespect to, e.g., FIGS. 1B and 1C. For example, when the storage layer804 comprises a perovskite oxide, the field may induce some metal atomsinto an “up” or a “down” orientation (depending on the polarity of thecharge), thereby storing a logical “1” or “0”. In some embodiments, areading operation may be accomplished by forcing the cell capacitor,using the access transistor, into a particular state, e.g., a “0” state.If the cell capacitor already held a “0” state, relatively low or nodetectable current may flow through the output lines. On the other hand,if the cell held a “1” state, the metal atoms may be re-oriented, whichmay be accompanied by a pulse of current in the output as they pushelectrons out of the metal having the “down” side. The presence of thispulse can indicate that the cell held a “1”. Since this processoverwrites the cell, reading the FeRAM cell 1200 may be a destructiveprocess, and the cell may be re-written if it was changed.

FIG. 10 illustrates a perspective view of a semiconductor devicecomprising a FeRAM cell 1000 according to embodiments. The FeRAM cell1000 is similar to the FeRAM cell 900 (FIG. 9) and includes aferroelectric capacitor 800 integrated in the back end of the line(interconnect/metallization levels), except, the transistor in the frontend of the line is implemented as a fin field effect transistor (FinFET)for advanced technology nodes, e.g., sub 100 nm nodes. The FinFETtransistor comprises a fin-shaped channel extending horizontally betweena source 932 and a drain 934, and a gate 938 electrode that wraps topand side surfaces of the fin-shaped channel. The gate 938 can beelectrically connected to a word line and the drain 934 can beelectrically connected to a bit line through the ferroelectric capacitor800.

The FeRAM cells 900 (FIG. 9) and 1000 (FIG. 10) may be electricallyconnected to an integrated processor (CPU) and integrated in addition toor at least partially in lieu of SRAM and/or DRAM cells to form L2and/or L3 cache memory in the illustrated example computingarchitecture.

Additional Examples

1. A semiconductor device, comprising:

-   -   a capacitor comprising:        -   a polar layer comprising a base polar material doped with a            dopant, wherein the base polar material includes one or more            metal elements and one or both of oxygen or nitrogen, and            wherein the dopant comprises a metal element that is            different from the one or more metal elements and is present            at a concentration such that a ferroelectric switching            voltage of the capacitor is different from that of the            capacitor having the base polar material without being doped            with the dopant by more than about 100 mV,        -   first and second crystalline conductive oxide electrodes on            opposing sides of the polar layer, and        -   first and second barrier metal layers on respective ones of            the first and second crystalline conductive oxide electrodes            on opposing sides of the polar layer.

2. The semiconductor device of Embodiment 1, wherein the base polarmaterial comprises a base ferroelectric material, and wherein increasingthe concentration of the dopant decreases the ferroelectric switchingvoltage.

3. The semiconductor device of Embodiment 2, wherein the ferroelectricswitching voltage is lower than about 1200 mV.

4. The semiconductor device of Embodiment 1, wherein a remnantpolarization of the polar layer is different than that of the base polarmaterial without the dopant by more than about 5 μC/cm².

5. The semiconductor device of Embodiment 2, wherein the polar layer hasa perovskite crystal structure and comprises a ferroelectric oxidehaving a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein A and A′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein B and B′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein one or both of the A′ and the B′are dopants, wherein m, n and z are integers, and wherein one or both ofx and y are greater than zero.

6. The semiconductor device of Embodiment 2, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofBaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ and PbZrTiO₃.

7. The semiconductor device of Embodiment 2, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofPb(Mg,Nb)O₃, Pb(Mg,Nb)O₃, PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃,BaTiO₃—Bi(Zn(Nb,Ta))O₃, BaTiO₃—BaSrTiO₃, Bi_(1-x)La_(x)FeO₃,Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

8. The semiconductor device of Embodiment 2, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofLiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO, KNaSrBaNbO.

9. The semiconductor device of Embodiment 2, wherein the dopantcomprises a lanthanide element or niobium.

10. The semiconductor device of Embodiment 2, wherein the baseferroelectric material has a hexagonal crystal structure, wherein thebase ferroelectric material comprises LuFeO₃ or has a chemical formularepresented by RMnO₃, and wherein R is a rare earth element.

11. The semiconductor device of Embodiment 2, wherein the baseferroelectric material comprises a superlattice comprising a first layeralternating with a second layer different from the first layer, whereinthe first layer has a chemical formula represented by ABO₃ and thesecond layer has a chemical formula represented by CDO₃, wherein A and Bare different metal elements and C and D are different metal elements,and wherein each of C and D are different from one or both of A and B.

12. The semiconductor device of Embodiment 11, wherein the first layercomprises SrTiO₃, and wherein the second layer comprises one or both ofPbTiO₃ and LaAlO₃.

13. The semiconductor device of Embodiment 2, wherein the polar layer isferroelectric and has a remnant polarization greater than about 10μC/cm².

14. The semiconductor device of Embodiment 1, wherein the polar layerhas a thickness less than about 50 nm.

15. The semiconductor device of Embodiment 2, wherein the dopant ispresent at a concentration such that the polar layer is paraelectric andhas substantially zero remnant polarization.

16. The semiconductor device of Embodiment 1, wherein the base polarmaterial comprises a dielectric material comprising one or more of Hf,Zr, Al, Si or Ga, wherein the dopant increases the ferroelectricity suchthat the polar layer has a remnant polarization greater than about 10μC/cm².

17. The semiconductor device of Embodiment 1, wherein one or both of thefirst and second metal layers comprises a refractory metal serving as adiffusion barrier.

18. The semiconductor device of Embodiment 1, further comprising atransistor, wherein the capacitor is electrically connected to a drainof the transistor.

19. The semiconductor device of Embodiment 18, wherein the polar layerhas the remnant polarization that is persistent for at least one day,such that the semiconductor device is a nonvolatile memory device.

20. A semiconductor device, comprising:

-   -   a capacitor comprising:        -   a polar layer comprising a base polar material doped with a            dopant, wherein the base polar material includes one or more            metal elements and one or both of oxygen or nitrogen, and            wherein the dopant comprises a metal element of one of 4d            series, 5d series, 4f series or 5f series that is different            from the one or more metal elements, wherein the dopant is            present at a concentration such that a remnant polarization            of the polar layer is different than that of the base polar            material without the dopant, and        -   first and second crystalline conductive oxide electrodes on            opposing sides of the polar layer; and    -   first and second barrier metal layers on respective ones of the        first and second crystalline conductive oxide electrodes on        opposing sides of the polar layer.

21. The semiconductor device of Embodiment 20, wherein the remnantpolarization of the polar layer is different from that of the base polarmaterial without the dopant by more than about 5 μC/cm².

22. The semiconductor device of Embodiment 20, wherein a ferroelectricswitching voltage of the capacitor is different from that of thecapacitor having the base polar material without being doped with thedopant by more than about 100 mV.

23. The semiconductor device of Embodiment 22, wherein the ferroelectricswitching voltage is lower than about 1200 mV.

24. The semiconductor device of Embodiment 20, wherein the polar layerhas one of a perovskite structure or hexagonal crystal structure.

25. The semiconductor device of Embodiment 24, wherein the dopantcomprises a lanthanide element or niobium.

26. The semiconductor device of Embodiment 20, wherein the polar layerhas a lattice constant that is matched within about 20% of a latticeconstant of one or both of the first and second crystalline conductiveoxide electrodes.

27. A semiconductor device, comprising:

-   -   a capacitor comprising:        -   a polar layer comprising a base polar material doped with a            dopant, wherein the base polar material includes one or more            metal elements and one or both of oxygen or nitrogen,            wherein the dopant comprises a metal element that is            different from the one or more metal elements and is present            at a concentration such that a remnant polarization of the            polar layer is different from that of the base polar            material without the dopant by more than about 5 μC/cm²,        -   first and second crystalline conductive oxide electrodes on            opposing sides of the polar layer, and        -   first and second barrier metal layers on respective ones of            the first and second crystalline conductive oxide electrodes            on opposing sides of the polar layer.

28. The semiconductor device of Embodiment 27, wherein the base polarmaterial comprises a base ferroelectric material, and wherein increasingthe concentration of the dopant decreases the remnant polarization ofthe base ferroelectric material.

29. The semiconductor device of Embodiment 27, wherein a ferroelectricswitching voltage of the capacitor is different from that of thecapacitor having the base polar material without being doped with thedopant by more than about 100 mV.

30. The semiconductor device of Embodiment 29, wherein the ferroelectricswitching voltage is lower than about 1200 mV.

31. A capacitor, comprising:

-   -   a crystalline polar layer comprising a base polar material        substitutionally doped with a dopant;    -   the base polar material comprising one or more metal elements        and one or both of oxygen or nitrogen; and    -   the dopant comprising a metal element of one of 4d series, 5d        series, 4f series or 5f series that is different from the one or        more metal elements, such that a ferroelectric switching voltage        of the capacitor is different from that of the capacitor having        the base polar material without being doped with the dopant by        more than about 100 mV.

32. The capacitor of Embodiment 31, wherein the base polar materialcomprises a base ferroelectric material, and wherein increasing theconcentration of the dopant decreases the ferroelectric switchingvoltage.

33. The capacitor of Embodiment 32, wherein the ferroelectric switchingvoltage is lower than about 1200 mV.

34. The capacitor of Embodiment 31, wherein the base polar materialcomprises a base ferroelectric material, and wherein increasing theconcentration of the dopant decreases the remnant polarization of thebase ferroelectric material.

35. The capacitor of Embodiment 32, wherein the polar layer has aperovskite crystal structure and comprises a ferroelectric oxide havinga chemical formula represented by A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z),wherein A and A′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein B and B′ occupy interchangeableatomic positions in the perovskite crystal structure, wherein one orboth of the A′ and the B′ are dopants, wherein m, n and z are integers,and wherein one or both of x and y are greater than zero.

36. The capacitor of Embodiment 32, wherein the polar layer comprises aferroelectric oxide selected from the group consisting of BaTiO₃,PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ and PbZrTiO₃.

37. The capacitor of Embodiment 32, wherein the polar layer comprises aferroelectric oxide selected from the group consisting of Pb(Mg,Nb)O₃,Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃ andBaTiO₃—BaSrTiO₃, Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ andBiFe_(1-y)Co_(y)O₃.

38. The capacitor of Embodiment 32, wherein the polar layer comprises aferroelectric oxide selected from the group consisting of LiNbO₃,LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO, KNaSrBaNbO.

39. The capacitor of Embodiment 38, wherein the dopant comprises alanthanide element or niobium.

40. The capacitor of Embodiment 32, wherein the base ferroelectricmaterial has a hexagonal crystal structure, wherein the baseferroelectric material comprises LuFeO₃ or has a chemical formularepresented by RMnO₃, and wherein R is a rare earth element.

41. The capacitor of Embodiment 32, wherein the base ferroelectricmaterial comprises a superlattice comprising a first layer alternatingwith a second layer different from the first layer, wherein the firstlayer has a chemical formula represented by ABO₃ and the second layerhas a chemical formula represented by CDO₃, wherein A and B aredifferent metal elements and C and D are different metal elements, andwherein each of C and D are different from one or both of A and B.

42. The capacitor of Embodiment 41, wherein the first layer comprisesSrTiO₃, and wherein the second layer comprises one or both of PbTiO₃ andLaAlO₃.

43. The capacitor of Embodiment 32, wherein the dopant is present at aconcentration such that the polar layer is paraelectric havingsubstantially zero remnant polarization.

44. The capacitor of Embodiment 31, wherein the base polar materialcomprises a dielectric material, wherein the dopant increases theferroelectricity of the dielectric material such that the polar layerhas a remnant polarization greater than about 10 μC/cm².

45. The capacitor of Embodiment 44, wherein the dielectric materialcomprises one or more of an oxide of Hf, Zr, Al, Si or a mixturethereof.

46. The capacitor of Embodiment 44, wherein the dielectric material hasa chemical formula represented by Hf_(1-x)E_(x)O_(y), wherein each of xand y is greater than zero, and wherein E is selected from the groupconsisting of Al, Ca, Ce, Dy, Er, Gd, Ge, La, Sc, Si, Sr, Sn or Y.

47. The capacitor of Embodiment 44, wherein the dielectric material hasa chemical formula represented by Al_(1-x)R_(x)N, Ga_(1-x)R_(x)N orAl_(1-x-y)Mg_(x)Nb_(y)N, wherein each of x and y is greater than zero,and wherein R is selected from the group consisting of Al, Ca, Ce, Dy,Er, Gd, Ge, La, Sc, Si, Sr, Sn or Y.

48. The capacitor of Embodiment 31, wherein the base polar materialcomprises a base paraelectric material, and wherein increasing theconcentration of the dopant increases the remnant polarization of thebase paraelectric material.

49. The capacitor of Embodiment 31, wherein the concentration of thedopant is graded in a layer normal direction of the polar layer.

50. A capacitor, comprising:

-   -   a crystalline polar layer comprising a base polar material        substitutionally doped with a dopant;    -   the base polar material comprising a base metal oxide having a        chemical formula ABO₃, wherein each of A and B represents one or        more metal elements occupying interchangeable atomic positions        of a crystal structure of the base polar material;    -   the dopant comprising a metal element of one of 4d series, 5d        series, 4f series or 5f series that different from the one or        more metal elements of the base polar material; and    -   first and second crystalline conductive oxide electrodes on        opposing sides of the polar layer,    -   wherein the crystalline polar layer has one of a perovskite        structure, a hexagonal crystal structure or a superlattice        structure.

51. The capacitor of Embodiment 50, wherein the base polar materialcomprises a base ferroelectric material, and wherein increasing theconcentration of the dopant decreases the remnant polarization of thebase ferroelectric material.

52. The capacitor of Embodiment 50, wherein a remnant polarization ofthe polar layer is different than that of the base polar materialwithout the dopant by more than about 5 μC/cm².

53. The capacitor of Embodiment 50, wherein a ferroelectric switchingvoltage of the capacitor is different from that of the capacitor havingthe base polar material without being doped with the dopant by more thanabout 100 mV.

54. The capacitor of Embodiment 53, wherein the ferroelectric switchingvoltage is lower than about 1200 mV.

55. The capacitor of Embodiment 50, wherein the base metal oxidecomprises a base ferroelectric metal oxide, and wherein increasing theconcentration of the dopant decreases the remnant polarization of thebase ferroelectric metal oxide.

56. The capacitor of Embodiment 55, wherein the dopant comprises alanthanide element or niobium.

57. The capacitor of Embodiment 56, wherein the dopant is present at aconcentration greater than 0 percent and less than 25 percent, andwherein the polar layer undergoes a ferroelectric transition at avoltage lower than about 1200 mV.

58. The capacitor of Embodiment 50, wherein the polar layer is a singlecrystal layer.

59. The capacitor of Embodiment 51, wherein the polar layer terminateswith a metal occupying a body center position of the perovskitestructure at one or both interfaces formed with one or both of the firstand second conductive oxide electrodes.

60. The capacitor of Embodiment 51, wherein the polar layer terminateswith a metal occupying corner positions of the perovskite structure atone or both interfaces formed with one or both of the first and secondconductive oxide electrodes.

61. A capacitor, comprising:

-   -   a crystalline polar layer comprising a base polar material        substitutionally doped with a dopant;    -   the base polar material comprising one or more metal elements        and one or both of oxygen or nitrogen; and    -   the dopant comprising a metal element of one of 4d series, 5d        series, 4f series or 5f series that is different from the one or        more metal elements, wherein the dopant is present at a        concentration such that a remnant polarization of the polar        layer is different than that of the base polar material without        the dopant by more than about 5 μC/cm².

62. The capacitor of Embodiment 61, wherein a ferroelectric switchingvoltage of the capacitor is different from that of the capacitor havingthe base polar material without being doped with the dopant by more thanabout 100 mV.

63. The capacitor of Embodiment 61, wherein the ferroelectric switchingvoltage is lower than about 1200 mV.

64. The capacitor of Embodiment 61, wherein the base metal oxidecomprises a base ferroelectric metal oxide, and wherein increasing theconcentration of the dopant decreases the remnant polarization of thebase ferroelectric metal oxide.

65. The capacitor of Embodiment 61, wherein the crystalline polar layerhas one of a perovskite structure, a hexagonal crystal structure or asuperlattice structure.

66. A semiconductor device, comprising:

-   -   a capacitor comprising:    -   a polar layer comprising a crystalline base polar material doped        with a dopant, wherein the base polar material includes one or        more metal elements and one or both of oxygen or nitrogen,        wherein the dopant comprises a metal element that is different        from the one or more metal elements and is present at a        concentration such that a ferroelectric switching voltage of the        capacitor is different from that of the capacitor having the        base polar material without being doped with the dopant by more        than about 100 mV, and    -   first and second crystalline conductive or semiconductive oxide        electrodes on opposing sides of the polar layer, wherein the        polar layer has a lattice constant that is matched within about        20% of a lattice constant of one or both of the first and second        crystalline conductive or semiconductive oxide electrodes,    -   wherein the first crystalline conductive or semiconductive oxide        electrode serves as a template for growing the polar layer        thereon, such that at least a portion of the polar layer is        pseudomorphically formed on the first crystalline conductive or        semiconductive oxide electrode.

67. The semiconductor device of Embodiment 66, wherein a ferroelectricswitching voltage of the capacitor is different from that of thecapacitor having the base polar material without being doped with thedopant by more than about 100 mV.

68. The semiconductor device of Embodiment 67, wherein the ferroelectricswitching voltage is lower than about 1200 mV.

69. The semiconductor device of Embodiment 66, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes have a thickness between about 1 nm and 5 nm.

70. The semiconductor device of Embodiment 67, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes have an electrical resistivity lower than 0.01 Ohms-cm.

71. The semiconductor device of Embodiment 66, wherein the polar layerand one or both of the first and second crystalline conductive orsemiconductive oxide electrodes have the same crystal structure.

72. The semiconductor device of Embodiment 71, wherein the dopantcomprises a lanthanide element or niobium.

73. The semiconductor device of Embodiment 72, wherein the polar layercomprises a region having a lateral dimension between about 10 nm and500 nm in which one or both of the first and second crystallineconductive or semiconductive oxide electrodes are pseudomorphic thereon.

74. The semiconductor device of Embodiment 71, wherein the same crystalstructure is a perovskite structure, and wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofBaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ PbZrTiO₃, Pb(Mg,Nb)O₃,Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃,BaTiO₃—BaSrTiO₃, LiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO, KNaSrBaNbO,Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

75. The semiconductor device of Embodiment 74, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes comprise an oxide selected from the group consisting of(La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃, YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃,SrRuO₃, LaMnO₃, SrMnO₃, LaCoO₃ or SrCoO₃.

76. The semiconductor device of Embodiment 75, wherein the polar layerdirectly contacts one or both of the first and second crystallineconductive or semiconductive oxide electrodes, and wherein thesemiconductor device further comprises a further electrode formed on oneor both of the first and second crystalline conductive or semiconductiveoxide electrodes and comprising a conductive binary metallic oxideselected from the group consisting of an iridium (Ir) oxide, a ruthenium(Ru) oxide, a palladium (Pd) oxide, an osmium (Os) oxide or a rhenium(Re) oxide.

77. The semiconductor device of Embodiment 71, wherein the same crystalstructure is a hexagonal crystal structure, wherein the polar layercomprises LuFeO₃ or has a chemical formula represented by RMnO₃, andwherein R is a rare earth element.

78. The semiconductor device of Embodiment 66, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes have one of a hexagonal structure, a delaffosite structure, aspinel structure or a cubic structure.

79. The semiconductor device of Embodiment 78, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes comprise one or more of PtCoO₂, PdCoO₂, Al-doped ZnO, Fe₃O₄,LiV₂O₄ or Sn-doped In₂O₃.

80. The semiconductor device of Embodiment 66, further comprising atransistor, wherein the capacitor is electrically connected to a drainof the transistor.

81. A semiconductor device, comprising:

-   -   a capacitor stack comprising:    -   a crystalline polar layer comprising a base polar material        substitutionally doped with a dopant;    -   the base polar material comprising a metal oxide having one of a        perovskite structure or a hexagonal crystal structure;    -   the dopant comprising a metal of one of 4d series, 5d series, 4f        series or 5f series that is different from metal(s) of the metal        oxide; and    -   first and second crystalline conductive or semiconductive oxide        electrodes on opposing sides of the crystalline polar layer,        wherein the crystalline polar layer has the same crystal        structure as one or both of the first and second crystalline        conductive or semiconductive oxide electrodes.

82. The semiconductor device of Embodiment 81, wherein the crystallinepolar layer has a lattice constant that is matched within about 20% of alattice constant of one or both of the first and second crystallineconductive oxide electrodes.

83. The semiconductor device of Embodiment 82, wherein the same crystalstructure is a perovskite crystal structure and the polar layercomprises a ferroelectric oxide having a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein A and A′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein B and B′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein one or both of the A′ and the B′are dopants, wherein m, n and z are integers, and wherein one or both ofx and y are greater than zero.

84. The semiconductor device of Embodiment 83, wherein one or both ofthe first and second crystalline conductive oxide electrodes comprisesan oxide having a chemical formula represented byC_((p-u))C′_(u)D_((q-v))D′_(v)O_(w), wherein C and C′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein D and D′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein p, q and w are integers, andwherein one or both of u and v are greater than zero.

85. The semiconductor device of Embodiment 84, wherein the polar layercomprises a ferroelectric oxide having a perovskite structure selectedfrom the group consisting of BaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃PbZrTiO₃, Pb(Mg,Nb)O₃, Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃,BaTiO₃—Bi(Zn(Nb,Ta))O₃, BaTiO₃—BaSrTiO₃, LiNbO₃, LiTaO₃, LiFeTaOF,SrBaNbO, BaNaNbO, KNaSrBaNbO, Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ andBiFe_(1-y)Co_(y)O₃.

86. The semiconductor device of Embodiment 85, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes comprise an oxide selected from the group consisting of(La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃, YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃,SrRuO₃, LaMnO₃, SrMnO₃, LaCoO₃ or SrCoO₃.

87. The semiconductor device of Embodiment 86, wherein the polar layerdirectly contacts one or both of the first and second crystallineconductive or semiconductive oxide electrodes, and wherein thesemiconductor device further comprises a further electrode formed on oneor both of first and second crystalline conductive or semiconductiveoxide electrodes and comprising a conductive binary metallic oxideselected from the group consisting of an iridium (Ir) oxide, a ruthenium(Ru) oxide, a palladium (Pd) oxide, an osmium (Os) oxide or a rhenium(Re) oxide.

88. The semiconductor device of Embodiment 82, wherein the same crystalstructure is a hexagonal crystal structure, wherein the polar layercomprises LuFeO₃ or has a chemical formula represented by RMnO₃, andwherein R is a rare earth element.

89. The semiconductor device of Embodiment 82, further comprising atransistor, wherein the capacitor is electrically connected to a drainof the transistor.

90. The semiconductor device of Embodiment 89, wherein the polar layerhas the remnant polarization that is persistent for at least one day,such that the semiconductor device is a nonvolatile memory device.

91. A semiconductor device, comprising:

-   -   a capacitor comprising:    -   a polar layer comprising a crystalline base polar material doped        with a dopant, wherein the base polar material includes one or        more metal elements and one or both of oxygen or nitrogen,        wherein the dopant comprises a metal element that is different        from the one or more metal elements and is present at a        concentration such that a remnant polarization of the polar        layer is different from that of the base polar material without        the dopant by more than about 5 μC/cm², and    -   first and second crystalline conductive or semiconductive oxide        electrodes on opposing sides of the polar layer, wherein the        polar layer has a lattice constant that is matched within about        20% of a lattice constant of one or both of the first and second        crystalline conductive or semiconductive oxide electrodes,    -   wherein the first crystalline conductive or semiconductive oxide        electrode serves as a template for growing the polar layer        thereon, such that at least a portion of the polar layer is        coherently strained on the first crystalline conductive or        semiconductive oxide electrode.

92. The semiconductor device of Embodiment 91, wherein the base polarmaterial comprises a base ferroelectric material, and wherein increasingthe concentration of the dopant decreases the remnant polarization ofthe base ferroelectric material.

93. The semiconductor device of Embodiment 91, wherein a ferroelectricswitching voltage of the capacitor is different from that of thecapacitor having the base polar material without being doped with thedopant by more than about 100 mV.

94. The semiconductor device of Embodiment 93, wherein the ferroelectricswitching voltage is lower than about 1200 mV.

95. The semiconductor device of Embodiment 91, wherein one or both ofthe first and second crystalline conductive or semiconductive oxideelectrodes comprise an oxide selected from the group consisting of(La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃, YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃,SrRuO₃, LaMnO₃, SrMnO₃, LaCoO₃ or SrCoO₃.

96. A semiconductor device, comprising:

-   -   a transistor formed on a silicon substrate; and    -   a capacitor electrically connected to the transistor by a        conductive via, the capacitor comprising:        -   upper and lower conductive oxide electrodes on opposing            sides of a polar layer, wherein the lower conductive oxide            electrode is electrically connected to a drain of the            transistor, and        -   a polar layer comprising a base polar material doped with a            dopant, wherein the base polar material includes one or more            metal elements and one or both of oxygen or nitrogen,            wherein the dopant comprises a metal element that is            different from the one or more metal elements and is present            at a concentration such that a ferroelectric switching            voltage of the capacitor is different from that of the            capacitor having the base polar material without being doped            with the dopant by more than about 100 mV; and    -   a lower barrier layer comprising a refractory metal or an        intermetallic compound between the lower conductive oxide        electrode and the conductive via.

97. The semiconductor device of Embodiment 96, wherein the polar layercomprises a metal oxide formed in an oxidizing environment at atemperature greater than 300° C.

98. The semiconductor device of Embodiment 96, further comprising anupper barrier layer comprising a refractory metal or an intermetalliccompound over the upper conductive oxide electrode.

99. The semiconductor device of Embodiment 96, wherein one or both ofthe upper and lower barrier layers comprise one or more of a Ti—Alalloy, a Ni—Al alloy, a Ni—Ti alloy, a Ni—Ga alloy, a Ni—Mn—Ga alloy, aFe—Ga alloy, a metal boride, a metal carbide, a metal nitride, Ta metal,W metal and Co metal.

100. The semiconductor device of Embodiment 96, wherein one or both ofthe upper and lower barrier layers comprises one or more of Ti₃Al, TiAl,TiAl₃, Ni₃Al, NiAl₃ NiAl, Ni₂MnGa, FeGa and Fe₃Ga.

101. The semiconductor device of Embodiment 96, further comprising abarrier sealant layer formed on one or both side surfaces of one or moreof the dielectric layer, the upper oxide electrode layer and the lowerconductive oxide electrode layer.

102. The semiconductor device of Embodiment 96, wherein the barriersealant layer comprises a metal oxide comprising Al or Mg.

103. The semiconductor device of Embodiment 96, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofBaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ PbZrTiO₃, Pb(Mg,Nb)O₃,Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃,BaTiO₃—BaSrTiO₃, LiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO, KNaSrBaNbO,Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

104. The semiconductor device of Embodiment 96, further comprising aninsulating sealant layer contacting one of both side surfaces of one ormore of the polar layer, the upper conductive oxide electrode and thelower conductive oxide electrode.

105. The semiconductor device of Embodiment 96, wherein the dopantcomprises a lanthanide element or niobium.

106. The semiconductor device of Embodiment 96, wherein the baseferroelectric material has a hexagonal crystal structure, wherein thebase ferroelectric material comprises LuFeO₃ or has a chemical formularepresented by RMnO₃, and wherein R is a rare earth element.

107. A semiconductor device, comprising:

-   -   a transistor formed on a silicon substrate;    -   a capacitor electrically connected to the transistor by a        conductive via, the capacitor comprising:        -   upper and lower conductive oxide electrodes on opposing            sides of a polar layer, wherein the lower conductive oxide            electrode is electrically connected to a drain of the            transistor, and        -   the polar layer comprising a base polar material doped with            a dopant, wherein the base polar material includes one or            more metal elements and one or both of oxygen or nitrogen,            and wherein the dopant comprises a metal element of one of            4d series, 5d series, 4f series or 5f series that is            different from metal(s) of the metal oxide that is present            at a concentration such that a remnant polarization of the            polar layer is different than that of the base polar            material without the dopant; and    -   a barrier sealant layer formed on one or both side surfaces of        one or more of the polar layer, the upper conductive oxide        electrode layer and the lower conductive oxide electrode layer.

108. The semiconductor device of Embodiment 107, wherein the polar layercomprises a metal oxide formed in an oxidizing environment at atemperature greater than 500° C.

109. The semiconductor device of Embodiment 108, wherein the barriersealant layer comprises a metal oxide.

110. The semiconductor device of Embodiment 109, wherein the barriersealant layer comprises a metal oxide of Al or Mg.

111. The semiconductor device of Embodiment 110, wherein the barriersealant layer comprises an oxide selected from the group consisting ofMgO, TiAlO or LaAlO.

112. The semiconductor device of Embodiment 108, wherein the barriersealant layer comprises oxidized, fluorinated and/or chlorinatedportions of one or more of the upper and lower conductive oxideelectrode layers and the polar layer.

113. The semiconductor device of Embodiment 108, further comprising oneor both of a lower barrier layer between the lower conductive oxideelectrode and the conductive via and an upper barrier layer over theupper conductive oxide electrode, wherein the one or both of the lowerand upper barrier layers comprise a refractory metal or an intermetalliccompound.

114. The semiconductor device of Embodiment 113, wherein one or both ofthe upper and lower barrier layers comprise one or more of a Ti—Alalloy, a Ni—Al alloy, a Ni—Ti alloy, a Ni—Ga alloy, a Ni—Mn—Ga alloy, aFe—Ga alloy, a metal boride, a metal carbide, a metal nitride, Ta metal,W metal and Co metal.

115. The semiconductor device of Embodiment 108, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofBaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ and PbZrTiO₃.

116. The semiconductor device of Embodiment 108, further comprising aninsulating sealant layer contacting one of both side surfaces of one ormore of the polar layer, the upper conductive oxide electrode and thelower conductive oxide electrode.

117. The semiconductor device of Embodiment 108, wherein the polar layercomprises a ferroelectric oxide selected from the group consisting ofBaTiO₃, PbTiO₃, KNbO₃, NaTaO₃, BiFeO₃ PbZrTiO₃, Pb(Mg,Nb)O₃,Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃, Pb(Sc,Nb)O₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃,BaTiO₃—BaSrTiO₃, LiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO, KNaSrBaNbO,Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

118. The semiconductor device of Embodiment 108, wherein the dopantcomprises a lanthanide element or niobium.

119. The semiconductor device of Embodiment 108, wherein the baseferroelectric material has a hexagonal crystal structure, wherein thebase ferroelectric material comprises LuFeO₃ or has a chemical formularepresented by RMnO₃, and wherein R is a rare earth element.

120. The semiconductor device of Embodiment 108, wherein one or both ofthe upper and lower conductive oxide electrodes comprise an oxideselected from the group consisting of (La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃,YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃, SrRuO₃, LaMnO₃, SrMnO₃, LaCoO₃ orSrCoO₃.

121. A semiconductor device, comprising:

-   -   a capacitor comprising a ferroelectric oxide layer interposed        between first and second conductive oxide electrode layers,        wherein the ferroelectric oxide layer comprises a base        ferroelectric oxide that is doped with a dopant, wherein the        dopant lowers a remnant polarization of the base ferroelectric        oxide relative to an undoped base ferroelectric oxide by at        least 5%.

122. A semiconductor device, comprising:

-   -   a ferroelectric oxide layer interposed between first and second        conductive oxide electrode layers, wherein the ferroelectric        oxide layer has a lattice constant that is matched within about        20% of a lattice constant of one or both of the first and second        conductive oxide electrode layers.

123. A semiconductor device, comprising:

-   -   a capacitor comprising a ferroelectric oxide layer interposed        between first and second conductive oxide electrode layers,        wherein the ferroelectric oxide layer undergoes a ferroelectric        transition at a voltage lower than about 600 mV.

124. A semiconductor device, comprising:

-   -   a capacitor comprising a ferroelectric oxide layer interposed        between first and second conductive oxide electrode layers,        wherein the ferroelectric oxide layer has a thickness less than        about 50 nm.

125. A semiconductor device, comprising:

-   -   a ferroelectric oxide layer having a remnant polarization        greater than about 10 μC/cm², wherein the ferroelectric oxide        layer is doped with a lanthanide element at a concentration        greater than about 5.0% on the basis of a total number of atomic        sites of a metal of the ferroelectric oxide layer.

126. The semiconductor device of Embodiment 121, wherein the baseferroelectric oxide has a remnant polarization greater than about 10μC/cm².

127. The semiconductor device of any one of Embodiments 121-126, whereinthe ferroelectric oxide layer undergoes a ferroelectric phase transitionat a voltage lower than about 200 mV.

128. The semiconductor device of any one of Embodiments 121-127, whereinthe ferroelectric oxide layer has a thickness between about 2 nm and 200nm.

129. The semiconductor device of any one of Embodiments 121-128, whereinthe ferroelectric oxide layer has a crystal lattice structure that isthe same as a crystal lattice structure of one or both of the first andsecond conductive oxide electrode layers.

130. The semiconductor device of any one of Embodiments 121-129, whereinthe ferroelectric oxide layer has a lattice constant that is matchedwithin about 10% of a lattice constant of one or both of the first andsecond conductive oxide electrode layers.

131. The semiconductor device of any one of Embodiments 121-130, whereinthe ferroelectric oxide layer has a chemical formula represented by achemical formula represented by A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z),wherein A and A′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein B and B′ occupy interchangeableatomic positions in the perovskite crystal structure, wherein one orboth of the A′ and the B′ are dopants, wherein m, n and z are integers,and wherein one or both of x and y are greater than zero.

132. The semiconductor device of Embodiment 131, wherein the A′ is anelement of one of 4d series, 5d series, 4f series or 5f series.

133. The semiconductor device of any one of Embodiments 131 or 132,wherein the A′ is a lanthanide element.

134. The semiconductor device of any one of Embodiments 131-133, whereinthe dopant comprises La.

135. The semiconductor device of any one of Embodiments 131-134, whereinthe amount of A′ is between about 0.1 atomic % and 20 atomic % on thebasis of the amount of A and A′.

136. The semiconductor device of any one of Embodiments 131-135, whereinB′ is an element selected from the group consisting of Mn, Sc, Ti, V,Cr, Co, Ni, Cu and Zn.

137. The semiconductor device of any one of Embodiments 121-136, whereinone or both of the first and second crystalline conductive oxideelectrodes comprises an oxide having a chemical formula represented byC_((p-u))C′_(u)D_((q-v))D′_(v)O_(w), wherein C and C′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein D and D′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein p, q and w are integers, andwherein one or both of u and v are greater than zero.

138. The semiconductor device of any one of Embodiments 121-137, whereinone or both of the first and second conductive oxide electrode layershave a thickness between about 1 nm and 5 nm.

139. The semiconductor device of any one of Embodiments 121-138, whereinone or both of the first and second conductive oxide electrode layershave a resistivity lower than 0.01 Ohms-cm.

140. The semiconductor device of any one of Embodiments 121-139, whereinone or both of the first and second conductive oxide electrode layerscomprise one or more of an iridium (Ir) oxide, a ruthenium (Ru) oxide, apalladium (Pd) oxide, an osmium (Os) oxide, a rhenium (Re) oxide,(La,Sr)CoO₃, SrRuO₃, (La,Sr)MnO₃, YBa₂Cu₃O₇, Bi₂Sr₂CaCu₂O₈, LaNiO₃ andSrTiO₃.

141. The semiconductor device of any one of Embodiments 121-140, whereinthe ferroelectric oxide layer has a region having a lateral dimensionbetween about 10 nm and 500 nm in which one or both of the first andsecond conductive oxide electrode layers form pseudomorphic layersthereon.

142. The semiconductor device of any one of Embodiments 121-140, whereinthe ferroelectric oxide layer has a perovskite structure.

143. The semiconductor device of Embodiment 142, wherein the baseferroelectric oxide comprises Bi.

144. The semiconductor device of Embodiments 142 or 143, wherein thebase ferroelectric oxide comprises BiFeO₃.

145. The semiconductor device of any one of Embodiments 142-144, whereinthe ferroelectric oxide layer comprises one of Bi_(1-x)La_(x)FeO₃,Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

146. The semiconductor device of Embodiment 142, wherein the baseferroelectric oxide comprises Pb.

147. The semiconductor device of Embodiments 142 or 146, wherein thebase ferroelectric oxide comprises PbTiO₃.

148. The semiconductor device of any one of Embodiments 142, 146 and147, wherein the ferroelectric oxide layer comprises PbTi_(1-y)Zr_(y)O₃or PbTi_(1-y-z)Zr_(y)Nb_(z)O₃, wherein each of y and z is greater thanzero.

149. The semiconductor device of any one of Embodiments 142-148, whereinone or both of the first and second conductive oxide electrode layerscomprise one or more of SrRuO₃, (La,Sr)MnO₃ and Nb-doped SrTiO₃.

150. The semiconductor device of any one of Embodiments 142-149, whereinthe ferroelectric oxide layer terminates with a metal occupying a bodycenter position of the perovskite structure at one or both interfacesformed with one or both of the first and second conductive oxideelectrode layers.

151. The semiconductor device of any one of Embodiments 142-149, whereinthe ferroelectric oxide layer terminates with a metal occupying cornerpositions of the perovskite structure at one or both interfaces formedwith one or both of the first and second conductive oxide electrodelayers.

152. The semiconductor device of any one of Embodiments 141-141, whereinthe ferroelectric oxide layer has a hexagonal structure.

153. The semiconductor device of Embodiment 152, wherein the baseferroelectric oxide comprises Mn.

154. The semiconductor device of Embodiments 152 or 153, wherein thebase ferroelectric oxide comprises AMnO₃, wherein A is an elementselected from the group consisting of cerium (Ce), dysprosium (Dy),erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum(La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), promethium (Pm),samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium(Yb), and yttrium (Y).

155. The semiconductor device of any one of Embodiments 152-154, whereinone or both of the first and second conductive oxide electrode layerscomprises Ir₂O₃ or IrO₂,

156. The semiconductor device of any one of Embodiments 121-141, whereinthe ferroelectric oxide layer comprises an improper ferroelectricmaterial in which a spontaneous polarization is accompanied by astructural phase transition.

157. The semiconductor device of Embodiment 156, wherein the baseferroelectric oxide layer comprises Lu.

158. The semiconductor device of Embodiments 156 or 157, wherein thebase ferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with another oxide.

159. The semiconductor device of any one of Embodiments 156-158, whereinthe base ferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with PbTiO₃.

160. The semiconductor device of any one of Embodiments 156-158, whereinthe base ferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with LaAlO₃.

161. The semiconductor device of any one of Embodiments 121-160, whereinupon application of an electric field, the ferroelectric oxide layerenergetically fluctuates between local minima of a double potential wellseparated by an energy barrier less than about 250 mV.

162. The semiconductor device of any one of Embodiments 121-161, whereinone or both of the first and second conductive oxide electrode layershave formed thereon a barrier layer formed on a side opposite theferroelectric oxide layer.

163. The semiconductor device of Embodiment 162, wherein the barrierlayer comprises a refractory metal or an intermetallic compound.

164. The semiconductor device of Embodiments 162 or 163, wherein thebarrier layer comprises one or more of a Ti—Al alloy, a Ni—Al alloy, aNi—Ti alloy, a Ni—Ga alloy, a Ni—Mn—Ga alloy, a Fe—Ga alloy, a metalboride, a metal carbide, a metal nitride, Ta metal, W metal and Cometal.

165. The semiconductor device of any one of Embodiments 121-165, furthercomprising a side barrier layer contacting one of both side surfaces ofone or more of the ferroelectric oxide layer, the first oxide electrodelayer and the second conductive oxide electrode layer.

166. The semiconductor device of Embodiment 165, wherein the sidebarrier layer comprises a metal oxide.

167. The semiconductor device of Embodiments 165 or 166, wherein theside barrier layer comprises a metal oxide comprising Al or Mg.

168. The semiconductor device of any one of Embodiments 121-167, whereina remnant polarization of the ferroelectric oxide layer is nonvolatile.

169. The semiconductor device of any one of Embodiments 121-168, whereina remnant polarization of the ferroelectric oxide layer is volatile suchthat the ferroelectric oxide layer is paraelectric.

170. The semiconductor device of any one of Embodiments 121-169, whereinone or more of the ferroelectric oxide layer, the first oxide electrodelayer and the second conductive oxide electrode layer have a gradedcomposition in a vertical direction normal to a stacking direction.

171. The semiconductor device of any one of Embodiments 121-170, furthercomprising a transistor, wherein the capacitor is electrically connectedto a drain of the transistor.

172. A composition of matter, comprising:

-   -   a ferroelectric oxide layer having a remnant polarization        greater than about 10 μC/cm², wherein the ferroelectric oxide        layer comprises a base ferroelectric oxide that is doped with a        dopant comprising a lanthanide element at a concentration        greater than about 5.0% % on the basis of a total number of        atomic sites of a metal of the ferroelectric oxide layer.

173. The composition of Embodiment 172, wherein the ferroelectric oxidelayer undergoes a ferroelectric phase transition at a voltage lower thanabout 200 mV.

174. The composition of Embodiments 172 or 173, wherein theferroelectric oxide layer has a thickness between about 2 nm and 200 nm.

175. The composition of any one of Embodiments 172-174, wherein theferroelectric oxide layer has a chemical formula represented byA_((m-x))A′_(x)B_((n-y))B′_(y)O_(z), wherein A and A′ occupyinterchangeable atomic positions in the perovskite crystal structure,wherein B and B′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein one or both of the A′ and the B′are dopants, wherein m, n and z are integers, and wherein one or both ofx and y are greater than zero.

176. The composition of Embodiment 175, wherein the A′ is the lanthanideelement.

177. The composition of Embodiment 176, wherein the A′ is La.

178. The composition of any one of Embodiments 175-177, wherein theamount of A′ is between about 0.1 atomic % and 20 atomic % on the basisof the amount of A.

179. The composition of any one of Embodiments 175-177, wherein B′ is anelement selected from the group consisting of Mn, Sc, Ti, V, Cr, Co, Ni,Cu and Zn.

180. The composition of any one of Embodiments 172-179, wherein theferroelectric oxide layer has a perovskite structure.

181. The composition of Embodiment 180, wherein the base ferroelectricoxide comprises Bi.

182. The composition of Embodiments 180 or 181, wherein the baseferroelectric oxide comprises BiFeO₃.

183. The composition of any one of Embodiments 180-182, wherein theferroelectric oxide layer comprises one of Bi_(1-x)La_(x)FeO₃,Bi_(1-x)Ce_(x)FeO₃ and BiFe_(1-y)Co_(y)O₃.

184. The composition of Embodiment 180, wherein the base ferroelectricoxide comprises Pb.

185. The composition of Embodiment 184, wherein the base ferroelectricoxide comprises PbTiO₃.

186. The composition of Embodiments 184 or 185, wherein theferroelectric oxide layer comprises PbTi_(1-y)Zr_(y)O₃ orPbTi_(1-y-z)Zr_(y)Nb_(z)O₃, wherein each of y and z is greater thanzero.

187. The composition of any one of Embodiments 172-179, wherein theferroelectric oxide layer has a hexagonal structure.

188. The composition of Embodiment 187, wherein the base ferroelectricoxide comprises Mn.

189. The composition of Embodiments 187 or 188, wherein the baseferroelectric oxide comprises Yi_(1-x)Mn_(x)O₃

190. The composition of any one of Embodiments 172-179, wherein theferroelectric oxide layer comprises an improper ferroelectric materialin which a spontaneous polarization is accompanied by a structural phasetransition.

191. The composition of Embodiment 190, wherein the base ferroelectricoxide layer comprises Lu.

192. The composition of Embodiments 190 or 191, wherein the baseferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with another oxide.

193. The composition of any one of Embodiments 190-192, wherein the baseferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with PbTiO₃.

194. The composition of any one of Embodiments 190-192, wherein the baseferroelectric oxide comprises a superlattice comprising SrTiO₃alternating with LaAlO₃.

195. The composition of any one of Embodiments 172-194, wherein uponapplication of an electric field, the ferroelectric oxide layerenergetically fluctuates between local minima of a double potential wellseparated by an energy barrier less than about 250 mV.

196. The composition of any one of Embodiments 172-195, wherein aremnant polarization of the ferroelectric oxide layer is nonvolatile.

197. The composition of any one of Embodiments 172-196, wherein aremnant polarization of the ferroelectric oxide layer is volatile suchthat the ferroelectric oxide layer is paraelectric.

198. The semiconductor device of Embodiment 149, wherein one or both ofthe first and second conductive oxide electrode layers further comprisea conducting binary oxide, wherein the one or more of SrRuO₃,(La,Sr)MnO₃ and Nb-doped SrTiO₃ are interposed between the binary oxideand the ferroelectric oxide layer.

199. The semiconductor device of Embodiment 198, wherein the binaryoxide is selected from the group consisting of an iridium (Ir) oxide, aruthenium (Ru) oxide, a palladium (Pd) oxide, an osmium (Os) oxide and arhenium (Re) oxide.

200. The semiconductor device of any one of Embodiments 152-154, whereinone or both of the first and second conductive oxide electrode layerscomprise a hexagonal conductive oxide having a delafossite structure.

201. The semiconductor device of Embodiment 200, wherein the hexagonalconductive oxide having the delafossite structure includes one or moreof PtCoO₂, PdCoO₂, and Al-doped ZnO.

202. The semiconductor device of Embodiments 164, wherein the barrierlayer comprises one or more of Ti₃Al, TiAl, TiAl₃, Ni₃Al, NiAl₃ NiAl,Ni₂MnGa, FeGa and Fe₃Ga.

203. The semiconductor device of Embodiments 165 or 166, wherein theside barrier layer comprises an oxide selected from the group consistingof MgO, TiAlO and LaAlO.

204. The semiconductor device of Embodiment 165, wherein the sidebarrier layer comprises one or both sidewalls of one or more of thefirst and second conductive oxide electrode layers and the ferroelectricoxide layer that are passivated by oxidation, fluorination and/orchlorination.

205. The semiconductor device of Embodiment 125 or the composition ofmatter of Embodiment 172, wherein the ferroelectric oxide layer has achemical formula represented by A_((m-x))A′_(x)B_((n-y))B′_(y)O_(z),wherein A and A′ occupy interchangeable atomic positions in theperovskite crystal structure, wherein B and B′ occupy interchangeableatomic positions in the perovskite crystal structure, wherein one orboth of the A′ and the B′ are dopants, wherein m, n and z are integers,and wherein one or both of x and y are greater than zero.

206. The semiconductor device of Embodiment 205 or the composition ofmatter of Embodiment 85, wherein the dopant element is present at aconcentration greater than about 12.5% on the basis of the total numberof atomic sites of the metal of the ferroelectric oxide layer.

207. The semiconductor device of Embodiment 205 or the composition ofmatter of Embodiment 85, wherein the metal of the ferroelectric oxidelayer is Bi.

208. The semiconductor device of Embodiment 205 or the composition ofmatter of Embodiment 85, wherein the ferroelectric oxide layer isBiFeO₃.

209. The semiconductor device, the capacitor or the composition of anyone of Embodiments 1-120, wherein the dopant occupies an atomic latticeposition that is interchangeable with a metal of the base polarmaterial, and wherein in the polar layer, the dopant has an oxidationstate that is different from the metal in the base polar material.

Aspects of this disclosure can be implemented in various electronicdevices. Examples of the electronic devices can include, but are notlimited to, consumer electronic products, parts of the consumerelectronic products, electronic test equipment, cellular communicationsinfrastructure such as a base station, etc. Examples of the electronicdevices can include, but are not limited to, a mobile phone such as asmart phone, a wearable computing device such as a smart watch or an earpiece, a telephone, a television, a computer monitor, a computer, amodem, a hand-held computer, a laptop computer, a tablet computer, apersonal digital assistant (PDA), a microwave, a refrigerator, avehicular electronics system such as an automotive electronics system, astereo system, a DVD player, a CD player, a digital music player such asan MP3 player, a radio, a camcorder, a camera such as a digital camera,a portable memory chip, a washer, a dryer, a washer/dryer, peripheraldevice, a clock, etc. Further, the electronic devices can includeunfinished products. Aspects of this disclosure can be particularlyimplemented in various wireless telecommunication technologies in whichhigh power, high frequency bands, improved linearity and/or improvedefficiency are desired, including military and space applications suchas radars, community antenna television (CATV), radar jammers andwireless telecommunication base-stations, to name a few.

Unless the context clearly requires otherwise, throughout thedescription and the claims, the words “comprise,” “comprising,”“include,” “including” and the like are to be construed in an inclusivesense, as opposed to an exclusive or exhaustive sense; that is to say,in the sense of “including, but not limited to.” The word “coupled”, asgenerally used herein, refers to two or more elements that may be eitherdirectly connected, or connected by way of one or more intermediateelements. Likewise, the word “connected”, as generally used herein,refers to two or more elements that may be either directly connected, orconnected by way of one or more intermediate elements. Additionally, thewords “herein,” “above,” “below,” and words of similar import, when usedin this application, shall refer to this application as a whole and notto any particular portions of this application. Where the contextpermits, words in the above Detailed Description using the singular orplural number may also include the plural or singular number,respectively. The word “or” in reference to a list of two or more items,that word covers all of the following interpretations of the word: anyof the items in the list, all of the items in the list, and anycombination of the items in the list.

Moreover, conditional language used herein, such as, among others,“can,” “could,” “might,” “may,” “e.g.,” “for example,” “such as” and thelike, unless specifically stated otherwise, or otherwise understoodwithin the context as used, is generally intended to convey that certainembodiments include, while other embodiments do not include, certainfeatures, elements and/or states. Thus, such conditional language is notgenerally intended to imply that features, elements and/or states are inany way required for one or more embodiments or whether these features,elements and/or states are included or are to be performed in anyparticular embodiment.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the disclosure. Indeed, the novel apparatus, methods, andsystems described herein may be embodied in a variety of other forms;furthermore, various omissions, substitutions and changes in the form ofthe methods and systems described herein may be made without departingfrom the spirit of the disclosure. For example, while blocks arepresented in a given arrangement, alternative embodiments may performsimilar functionalities with different components and/or circuittopologies, and some blocks may be deleted, moved, added, subdivided,combined, and/or modified. Each of these blocks may be implemented in avariety of different ways. Any suitable combination of the elements andacts of the various embodiments described above can be combined toprovide further embodiments. The various features and processesdescribed above may be implemented independently of one another, or maybe combined in various ways. All possible combinations andsubcombinations of features of this disclosure are intended to fallwithin the scope of this disclosure.

What is claimed is:
 1. A capacitor, comprising: a crystallineparaelectric layer comprising a base ferroelectric oxide layer that issubstitutionally doped with a dopant; wherein the dopant comprises ametal element of one of 4f series or 5f series that is different fromand substitutionally replaces one or more metal elements of theferroelectric oxide and is present at a concentration, such that theparaelectric layer exhibits a polarization that depends nonlinearly onelectric field without a substantial hysteresis or remnant polarization.2. The capacitor of claim 1, wherein the dopant has an oxidation statethat is the same as an oxidation state of a metal element in the baseferroelectric oxide layer the dopant substitutionally replaces.
 3. Thecapacitor of claim 1, wherein the paraelectric layer does not undergoferroelectric switching under an electric field, and wherein theferroelectric oxide layer without the dopant has a switching voltagethat is greater than zero and lower than about 1200 mV.
 4. The capacitorof claim 1, wherein the paraelectric layer has a perovskite crystalstructure and comprises a ferroelectric oxide having a chemical formularepresented by A_((m-x))A′_(X)B_((n-y))B′_(y)O_(z), wherein A and A′occupy interchangeable atomic positions in the perovskite crystalstructure, wherein B and B′ occupy interchangeable atomic positions inthe perovskite crystal structure, wherein one or both of the A′ and theB′ are dopants, wherein m, n and z are integers, and wherein one or bothof x and y are greater than zero.
 5. The capacitor of claim 4, whereinthe base ferroelectric layer comprises a ferroelectric oxide selectedfrom the group consisting of BaTiO₃, BaTiO₃—Bi(Zn(Nb,Ta))O₃ andBaTiO₃—BaSrTiO₃.
 6. The capacitor of claim 5, wherein the dopantreplaces Ba.
 7. The capacitor of claim 4, wherein the base ferroelectriclayer comprises a ferroelectric oxide selected from the group consistingof BiFeO₃ and Bi_(1-x)La_(x)FeO₃, Bi_(1-x)Ce_(x)FeO₃ andBiFe_(1-y)Co_(y)O₃ and BaTiO₃—Bi(Zn(Nb,Ta))O₃.
 8. The capacitor of claim7, wherein the dopant replaces Bi.
 9. The capacitor of claim 4, whereinthe base ferroelectric layer comprises a ferroelectric oxide selectedfrom the group consisting of PbTiO₃, PbZrTiO₃, Pb(Mg,Nb)O₃,Pb(Mg,Nb)O₃—PbTiO₃, PbLaZrTiO₃ and Pb(Sc,Nb)O₃.
 10. The capacitor ofclaim 9, wherein the dopant replaces Pb.
 11. The capacitor of claim 4,wherein the polar layer comprises a ferroelectric oxide selected fromthe group consisting of LiNbO₃, LiTaO₃, LiFeTaOF, SrBaNbO, BaNaNbO,KNaSrBaNbO, KNbO₃ and NaTaO₃.
 12. The capacitor of claim 4, wherein thedopant comprises a lanthanide element.
 13. The capacitor of claim 1,wherein the dopant comprises lanthanum.
 14. The capacitor of claim 1,wherein the base ferroelectric oxide has a hexagonal crystal structure,wherein the base ferroelectric material comprises LuFeO₃.
 15. Thecapacitor of claim 1, wherein the base ferroelectric oxide has ahexagonal crystal structure and has a chemical formula represented byRMnO₃, and wherein R is a rare earth element.
 16. The capacitor of claim1, wherein the base ferroelectric oxide comprises a superlatticecomprising a first layer alternating with a second layer different fromthe first layer, wherein the first layer has a chemical formularepresented by ABO₃ and the second layer has a chemical formularepresented by CDO₃, wherein A and B are different metal elements and Cand D are different metal elements, and wherein each of C and D aredifferent from one or both of A and B.
 17. The capacitor of claim 16,wherein the first layer comprises SrTiO₃, and wherein the second layercomprises one or both of PbTiO₃ and LaAlO₃.
 18. The capacitor of claim1, wherein the concentration of the dopant is graded in a layer normaldirection of the paraelectric layer.
 19. A capacitor, comprising: acrystalline paraelectric layer comprising a base ferroelectric oxidelayer that is substitutionally doped with a dopant; the baseferroelectric oxide layer having a chemical formula ABO₃, wherein eachof A and B represents one or more metal elements occupying atomicpositions of a crystal structure of the base ferroelectric oxide layerthat can be substitutionally replaced by the dopant; the dopantcomprising a metal element of one of 4f series or 5f series that aresubstituting the one or more of A and B at a concentration such that theparaelectric layer exhibits a polarization that depends nonlinearly onelectric field without a substantial hysteresis or remnant polarization;and first and second crystalline conductive oxide electrodes on opposingsides of the paraelectric layer.
 20. The capacitor of claim 19, whereinthe dopant has an oxidation state that is the same as an oxidation stateof a metal in the base ferroelectric oxide layer the dopantsubstitutionally replaces.
 21. The capacitor of claim 19, wherein thecrystalline paraelectric layer has one of a perovskite structure, ahexagonal crystal structure or a superlattice structure.
 22. Thecapacitor of claim 21, wherein the paraelectric layer does not undergoferroelectric switching under an electric field, and wherein theferroelectric oxide layer without the dopant has a switching voltagethat is greater than zero and lower than about 1200 mV.
 23. Thecapacitor of claim 21, wherein the dopant comprises a lanthanide elementor niobium.
 24. The capacitor of claim 23, wherein the dopant is presentat a concentration greater than 0 percent and less than 25 percent. 25.The capacitor of claim 19, wherein the crystalline paraelectric layer isa single crystal layer.